Modeling of surface phenomena of liquid Al-Ni alloys using molecular dynamics.

This work presents a study on the surface tension of liquid Aluminum-Nickel (Al-Ni) alloys. Obtaining adequate values of surface tension for this system is not a simple task as these alloys present the formation of atomic clusters with short-range order at certain compositions, which dramatically influences surface tension. The Compound Forming Model predicts the influence of these clusters on surface tension, but experimental limitations have obstructed its validation due to deficient thermodynamic data. This work attempts to overcome some of these limitations by using Molecular Dynamics (MD). By comparing the obtained results from MD simulations with those of an equivalent system without clusters, it was possible to infer the role of the atomic clusters on Al-Ni surface tension. It was found that these clusters increase surface tension by decreasing the Al content at the surface. They achieve this reduction in Al content at the surface by trapping Al atoms and hindering their travel to the surface.

Internal and interfacial microstructure characterization of ice droplets on surfaces by X-ray computed tomography.

HYPOTHESIS: Characterizing the microstructure of an ice/surface interface and its effect on the icephobic behavior of surfaces remains a significant challenge. Introducing X-ray Computed Tomography (XCT) can provide unprecedented insights into the internal (porosity) and interfacial structures, i.e. wetting regime, between (super)hydrophobic surfaces and ice by visualizing these optically inaccessible regions. EXPERIMENTS: Frozen droplets with controlled volume were deposited on top of metallic and polymeric substrates with different levels of wettability. Different modes of XCT (3D and 4D) were utilized to obtain information on the internal and interfacial structure of the ice/surface system. The results were supplemented by conventional surface analysis techniques, including optical profilometry and contact angle measurements. FINDINGS: Using XCT on ice/surface systems, the 3D and 4D (imaging with temporal resolution) structural information can be visualized. From these datasets, qualitative and quantitative results were obtained, not only for characterizing the interface but also for analyzing the entire droplet/surface system, e.g., measurement of porosity size, shape, and location. These results highlight the potential of XCT in the characterization of both droplets and substrates and proves that the technique can aid to develop hydrophobic surfaces for use as icephobic materials.

Dynamic wetting of various liquids: Theoretical models, experiments, simulations and applications.

Dynamic wetting is a ubiquitous phenomenon and frequently observed in our daily life, as exemplified by the famous lotus effect. It is also an interfacial process of upmost importance involving many cutting-edge applications and has hence received significantly increasing academic and industrial attention for several decades. However, we are still far away to completely understand and predict wetting dynamics for a given system due to the complexity of this dynamic process. The physics of moving contact lines is mainly ascribed to the full coupling with the solid surface on which the liquids contact, the atmosphere surrounding the liquids, and the physico-chemical characteristics of the liquids involved (small-molecule liquids, metal liquids, polymer liquids, and simulated liquids). Therefore, to deepen the understanding and efficiently harness wetting dynamics, we propose to review the major advances in the available literature. After an introduction providing a concise and general background on dynamic wetting, the main theories are presented and critically compared. Next, the dynamic wetting of various liquids ranging from small-molecule liquids to simulated liquids are systematically summarized, in which the new physical concepts (such as surface segregation, contact line fluctuations, etc.) are particularly highlighted. Subsequently, the related emerging applications are briefly presented in this review. Finally, some tentative suggestions and challenges are proposed with the aim to guide future developments.

Comparing the Replication Fidelity of Solid Microneedles Using Injection Compression Moulding and Conventional Injection Moulding.

Polymer surfaces are increasingly being functionalized with micro- and nano- surface features using mass replication methods such as injection moulding. An example of these are microneedle arrays, which contain needle-like microscopic structures, which facilitate drug or vaccine delivery in a minimally invasive way. In this study, the replication fidelity of two types of solid polycarbonate microneedles was investigated using injection compression moulding and conventional injection moulding. Using a full factorial design of experiments for the injection moulding process, it was found that the volumetric injection rate had the largest positive effect on the replication fidelity. The mould temperature and holding pressure were also found to have a positive effect, while the effect of the melt temperature was found to be insignificant for the considered temperature range. For the injection compression moulding process, it was found that a larger compression stroke resulted in a better replication fidelity. A comparison between the replication fidelity for the injection moulding and injection compression moulding indicated that the injection compression moulding process resulted in a higher and more uniform replication fidelity. Using finite element flow simulations, a higher and more evenly distributed cavity pressure was observed compared to the conventional injection moulding process.

Cellulose Nanocrystals: Tensile Strength and Failure Mechanisms Revealed Using Reactive Molecular Dynamics.

Cellulose nanocrystals (CNCs) offer excellent mechanical properties. However, measuring the strength by performing reliable experiments at the nanoscale is challenging. In this paper, we model Iß crystalline cellulose using reactive molecular dynamics simulations. Taking the fibril twist into account, structural changes and hydrogen-bonding characteristics of CNCs during the tensile test are inspected and the failure mechanism of CNCs is analyzed down to the scale of individual bonds. The C4-O4 glycosidic bond is found to be responsible for the failure of CNCs. Finally, the effect of strain rate on ultimate properties is analyzed and a nonlinear model is used to predict the ultimate strength of 9.2 GPa and ultimate strain of 8.5% at a 1 s-1 strain rate. This study sheds light on the applications of cellulose in nanocomposites and further modeling of cellulose nanofibres.

Cellulose-hemicellulose interactions - A nanoscale view.

In this work, we study interactions of five different hemicellulose models, i.e. Galactoglucomannan, O-Acetyl-Galactoglucomannan, Fuco-Galacto-Xyloglucan, 4-O-Methylglucuronoxylan, and 4-O-Methylglucuronoarabinoxylan, and their respective binding strength to cellulose nanocrystals by molecular dynamics simulations. Glucuronoarabinoxylan showed the highest free energy of binding, whereas Xyloglucan had the lowest interaction energies amongst the five models. We further performed simulated shear tests and concluded that failure mostly happens at the inter-molecular interaction level within the hemicellulose fraction, rather than at the interface with cellulose. The presence of water molecules seems to have a weakening effect on the interactions of hemicellulose and cellulose, taking up the available hydroxyl groups on the surface of the cellulose for hydrogen bonding. We believe that these studies can shed light on better understanding of plant cell walls, as well as providing evidence on variability of the structures of different plant sources for extractions, purification, and operation of biorefineries.

Carbon Nanotube Fibers Decorated with MnO2 for Wire-Shaped Supercapacitor.

Fibers made from CNTs (CNT fibers) have the potential to form high-strength, lightweight materials with superior electrical conductivity. CNT fibers have attracted great attention in relation to various applications, in particular as conductive electrodes in energy applications, such as capacitors, lithium-ion batteries, and solar cells. Among these, wire-shaped supercapacitors demonstrate various advantages for use in lightweight and wearable electronics. However, making electrodes with uniform structures and desirable electrochemical performances still remains a challenge. In this study, dry-spun CNT fibers from CNT carpets were homogeneously loaded with MnO2 nanoflakes through the treatment of KMnO4. These functionalized fibers were systematically characterized in terms of their morphology, surface and mechanical properties, and electrochemical performance. The resulting MnO2-CNT fiber electrode showed high specific capacitance (231.3 F/g) in a Na2SO4 electrolyte, 23 times higher than the specific capacitance of the bare CNT fibers. The symmetric wire-shaped supercapacitor composed of CNT-MnO2 fiber electrodes and a PVA/H3PO4 electrolyte possesses an energy density of 86 nWh/cm and good cycling performance. Combined with its light weight and high flexibility, this CNT-based wire-shaped supercapacitor shows promise for applications in flexible and wearable energy storage devices.

Tensile behaviour of dislocated/crystalline cellulose fibrils at the nano scale.

Atomistic modelling of cellulose has widely been investigated for years using molecular dynamics simulations. In this paper, we model Iß crystalline cellulose as well as develop a model including dislocations in between the crystal regions. The model including dislocations shows a tensile modulus of 109 GPa, 25% lower than that of the fully crystalline model (146 GPa). The change in dihedral angle preferences is analysed, and its effect on hydrogen bonding pattern is assessed. How presence of hydrogen bonds contributes to elastic properties of cellulose nano-fibrils is shown. Effect of water on the elastic modulus of fibrils is also investigated. Moreover, an illustration is given of how the tensile behaviour of fibrils is controlled by a synergy between the geometry changes occurring at the glycosidic linkage, reflected by specific torsional and glycosidic angles. These findings can be useful in further modelling of cellulosic fibrils at the atomistic and coarse-grained scales.

Wetting dynamics and surface energy components of single carbon fibers.

HYPOTHESIS: Measuring contact angles made by liquids around individual carbon fibers (CFs) using the Wilhelmy technique is a conventional method to evaluate their surface properties. However, despite its apparent simplicity, inaccurate measurements of capillary forces and wetted lengths, due to the fineness of the CFs, as well as an improper selection of probe liquids can lead to incorrect contact angle and surface energy calculations, leading to an erroneous characterization of their surface properties. EXPERIMENTS: In this study, dynamic wetting experiments of individual CFs were performed in ethylene glycol, diiodomethane, and formamide based on the Wilhelmy method. Capillary forces exerted on the CFs were recorded and analyzed in detail to calculate reliable dynamic contact angles at different contact-line velocities. The molecular-kinetic theory (MKT) and hydrodynamic approach (HD) were then used to model the experimental data and to obtain static contact angles. FINDINGS: The analysis shows that the experimental data are in good agreement with the linear MKT suggesting that the dominant channel of energy dissipation at the contact line is the contact-line friction. From the predicted static advancing contact angle values, the surface energy components of the CFs could be obtained thus providing a way to characterize their interfacial properties and predict their compatibility with polymer matrices. This study furthermore points out the importance of choosing the correct combination of test fluids to obtain reliable surface energy results.

Wettability and Interfacial Properties of Carbon Fiber and Poly(ether ether ketone) Fiber Hybrid Composite.

Studies on carbon fiber (CF)/poly(ether ether ketone) (PEEK) fiber hybrid textiles were initiated several decades ago because their flexibility and conformability make them a promising alternative to traditional prepregs. The adhesion between the CFs and PEEK is mostly controlled by their inherent surface properties and mutual wettability. However, details of these properties remain largely unknown, especially those of PEEK. Therefore, to determine the surface and interfacial properties of these fibers, we performed a comprehensive study and characterized their surface topography (atomic force microscopy, scanning electron microscopy), surface chemistry [X-ray photoelectron spectrometry (XPS), acid-base titration], surface energies (wetting tests, acid-base approach), and interfacial mechanical properties [droplet test, interfacial shear strength (IFSS)]. These experiments were complemented by a theoretical approach to the prediction of the surface energy components (parachor) and contact angles of PEEK. We found good agreement between the results obtained by XPS and wetting tests (base-to-acid surface energy component ratio), as well as between the predicted and measured surface energy and contact angles. The results highlight the consistency and reliability of the proposed methodology. We found that both CFs and PEEK fibers appear to be smooth at the nanoscale and have large dispersive and basic surface energy components. The IFSS of CF/PEEK is significantly higher (44.87 ± 5.76 MPa) compared to that of other thermoplastic systems. The findings not only demonstrate the potential of CF/PEEK hybrid textiles but also emphasize the need to further increase the compatibility between CFs and PEEK fibers by increasing the acidic component of CF surfaces. Surface treatments and the design of a suitable sizing are potential methods to achieve this objective in future studies.

Self-Assembly of Hybrid Nanorods for Enhanced Volumetric Performance of Nanoparticles in Li-Ion Batteries.

The benefits of nanosize active particles in Li-ion batteries are currently ambiguous. They are acclaimed for enhancing the cyclability of certain electrode materials and for improving rate performance. However, at the same time, nanoparticles are criticized for causing side reactions as well as for their low packing density and, therefore, poor volumetric battery performance. This paper demonstrates for the first time that self-assembly can be used to pack nanoparticles into dense battery electrodes with up to 4-fold higher volumetric capacities. Furthermore, despite the dense packing of the self-assembled electrodes, they retain a higher volumetric capacity than randomly dispersed nanoparticles up to rates of 5 C. Finally, we did not observe substential degradation in capacity after 1000 cycles, and post-mortem analysis indicates that the self-assembled structures are maintained during cycling. Therefore, the proposed self-assembled electrodes profit from the advantages of nanostructured battery materials without compromising the volumetric performance.

Capillary rise of polydimethylsiloxane around a poly(ethylene terephthalate) fiber versus viscosity: Existence of a sharp transition in the dynamic wetting behavior.

HYPOTHESIS: Since the emergence of the molecular-kinetic theory and the hydrodynamic approach, it is generally accepted that the displacement of the contact line is controlled by the viscous or frictional channel of energy dissipation for respectively high-viscosity and low-viscosity liquids. However, how the dissipation switches from one channel to another is still unknown. We therefore hypothesized that, by progressively changing the viscosity of a liquid, a better understanding of the underlying mechanism driving this wetting dynamic transition would be obtained. EXPERIMENTS: Performing capillary rise experiments of polydimethylsiloxane on a poly(ethylene terephthalate) fiber at different temperatures, i.e. at different liquid viscosities, we characterized the transition between the viscous and frictional regimes. The fiber surface topography was also characterized and its effect on the wetting dynamics was quantified. FINDINGS: The wetting dynamics switched from one regime to the other in a very short viscosity interval. Besides, the wetting behavior in the transition region is sensitive to the fiber surface topography. The presence or the absence of a liquid rim ahead of the contact line actually determines the dominant channel of dissipation.

Wetting dynamics of polydimethylsiloxane mixtures on a poly(ethylene terephthalate) fiber.

HYPOTHESIS: The wetting dynamics of liquids with identical surface tensions are mostly controlled by their viscosities. We therefore hypothesized that the wetting dynamics of one- (pure liquid) and two-component (mixture) polydimethylsiloxane (PDMS) on a poly(ethylene terephthalate) (PET) fiber with similar surface tensions and viscosities should be controlled by the same underlying physical mechanisms. EXPERIMENTS: We studied the capillary rise of PDMS liquids on a PET fiber. We compared the different contact angle relaxations and characterized the transitions between the molecular-kinetic theory (MKT) and hydrodynamic approach (HD) for the PDMS mixtures and the pure liquids as a function of their viscosities. FINDINGS: Compared to the pure PDMS liquid with a viscosity of 20 mm2/s that presents a contact angle relaxation following a t-1/2 scale law in agreement with HD, the PDMS mixture with a higher viscosity (27.4 mm2/s) shows a t-1 behavior predicted by the MKT. Moreover, the transition between MKT and HD appears in a regime with higher viscosities for PDMS mixtures than for pure liquids. Surface segregation of shorter PDMS chains or precursor film may be responsible for this shift.

Spreading Dynamics of Molten Polymer Drops on Glass Substrates.

Wetting dynamics drive numerous processes involving liquids in contact with solid substrates with a wide range of geometries. The spreading dynamics of organic liquids and liquid metals at, respectively, room temperature and >1000 °C have been studied extensively, both experimentally and numerically; however, almost no attention has been paid to the wetting behavior of molten drops of thermoplastic polymers, despite its importance, for example, in the processing of fiber-reinforced polymer composites. Indeed, the ability of classical theories of dynamic wetting, that is, the hydrodynamic and the molecular-kinetic theories, to model these complex liquids is unknown. We have therefore investigated the spreading dynamics on glass, over temperatures between 200 and 260 °C, of two thermoplastics: polypropylene (PP) and poly(vinylidene fluoride) (PVDF). PP and PVDF showed, respectively, the highest and lowest slip lengths due to their different interactions with the glass substrate. The jump lengths of PP and PVDF are comparable to their Kuhn segment lengths, suggesting that the wetting process of these polymers is mediated by segmental displacements. The present work not only provides evidence of the suitability of the classical models to model dynamic wetting of molten polymers but also advances our understanding of the wetting dynamics of molten thermoplastics at the liquid/solid interface.

Wettability of a Single Carbon Fiber.

Wettability as determined from contact angle measurements is a suitable parameter for characterizing the physical bonding of a polymer matrix and reinforcing fibers, but it is very challenging to measure the capillary force exerted by a probe liquid on a fiber accurately for very fine fibers such as single carbon fibers. Herein, we propose an innovative method for measuring dynamic contact angles with a tensiometer, considering both the intrinsic variability of the carbon fiber diameter and the extremely small amplitude of the capillary forces, allowing the measurement of reliable dynamic contact angles over a large range of contact line velocities. The analysis of the contact angle dynamics by the molecular-kinetic theory permits us to check the relevancy of the measured contact angles and to obtain the static contact angle value, improving the prospect of employing tensiometry to better understand the wetting behavior of carbon fibers.

Young's equation at the nanoscale.

In 1805, Thomas Young was the first to propose an equation to predict the value of the equilibrium contact angle of a liquid on a solid. Today, the force exerted by a liquid on a solid, such as a flat plate or fiber, is routinely used to assess this angle. Moreover, it has recently become possible to study wetting at the nanoscale using an atomic force microscope. Here, we report the use of molecular-dynamics simulations to investigate the force distribution along a 15 nm fiber dipped into a liquid meniscus. We find very good agreement between the measured force and that predicted by Young's equation.

Drop impact on soft surfaces: beyond the static contact angles.

The wettability of cross-linked poly(dimethylsiloxane) elastomer films and of octadecyltrichlorosilane self-assembled monolayers with water has been measured and compared using various methods. Contact angle hysteresis values were compared with values reported in the literature. A new method to characterize advancing, receding contact angles, and hysteresis using drop impact have been tested and compared with usual methods. It has been found that for the rigid surfaces the drop impact method is comparable with other methods but that for elastomer surfaces the hysteresis is function of the drop impact velocity which influences the extent of the deformation of the soft surface at the triple line.

Superhydrophobic aluminum surfaces by deposition of micelles of fluorinated block copolymers.

Superhydrophobic surfaces are generated by chemisorption on aluminum substrates of fluorinated block copolymers synthesized by reversible addition-fragmentation chain transfer in supercritical carbon dioxide. In an appropriate solvent, those block copolymers can form micelles with a fluorinated corona, which are grafted on the aluminum substrate thanks to the presence of carboxylic acid groups in the corona. Water contact angle and drop impact analysis were used to characterize the wettability of the films at the macroscale, and atomic force microscopy measurements provided morphological information at the micro- and nanoscale. The simple solvent casting of the polymer solution on a hydroxylated aluminum surface results in a coating with multiscale roughness, which is fully superhydrophobic over areas up to 4 cm(2).

Dynamics of the rise around a fiber: experimental evidence of the existence of several time scales.

We study experimentally the dynamics of the spontaneous rise of a meniscus made of polydimethylsiloxane of various viscosities on the outside of a micrometric fiber made of monofilament in polyethyleneterephthalate. Optical methods are used to measure simultaneously the height of the liquid interface and the associated contact angle versus time. Versus the liquid viscosity, we observe asymptotically, for the dynamic contact angle, either a t(-1/2) behavior in agreement with the hydrodynamic description or a t(-1) behavior predicted by the molecular-kinetic theory, in its linear form, thus confirming the existence of at least two major time scales in the rise phenomenon.