Advances in Membrane Separation for Biomaterial Dewatering.

Biomaterials often contain large quantities of water (50-98%), and with the current transition to a more biobased economy, drying these materials will become increasingly important. Contrary to the standard, thermodynamically inefficient chemical and thermal drying methods, dewatering by membrane separation will provide a sustainable and efficient alternative. However, biomaterials can easily foul membrane surfaces, which is detrimental to the performance of current membrane separations. Improving the antifouling properties of such membranes is a key challenge. Other recent research has been dedicated to enhancing the permeate flux and selectivity. In this review, we present a comprehensive overview of the design requirements for and recent advances in dewatering of biomaterials using membranes. These recent developments offer a viable solution to the challenges of fouling and suboptimal performances. We focus on two emerging development strategies, which are the use of electric-field-assisted dewatering and surface functionalizations, in particular with hydrogels. Our overview concludes with a critical mention of the remaining challenges and possible research directions within these subfields.

Influence of Wettability and Geometry on Contact Electrification between Nonionic Insulators.

Contact electrification is an interfacial process in which two surfaces exchange electrical charges when they are in contact with one another. Consequently, the surfaces may gain opposite polarity, inducing an electrostatic attraction. Therefore, this principle can be exploited to generate electricity, which has been precisely done in triboelectric nanogenerators (TENGs) over the last decades. The details of the underlying mechanisms are still ill-understood, especially the influence of relative humidity (RH). Using the colloidal probe technique, we convincingly show that water plays an important role in the charge exchange process when two distinct insulators with different wettability are contacted and separated in <1 s at ambient conditions. The charging process is faster, and more charge is acquired with increasing relative humidity, also beyond RH = 40% (at which TENGs have their maximum power generation), due to the geometrical asymmetry (curved colloid surface vs planar substrate) introduced in the system. In addition, the charging time constant is determined, which is found to decrease with increasing relative humidity. Altogether, the current study adds to our understanding of how humidity levels affect the charging process between two solid surfaces, which is even enhanced up to RH = 90% as long as the curved surface is hydrophilic, paving the way for designing novel and more efficient TENGs, eco-energy harvesting devices which utilize water and solid charge interaction mechanism, self-powered sensors, and tribotronics.

Wetting of Two-Component Drops: Marangoni Contraction Versus Autophobing.

The wetting properties of multicomponent liquids are crucial to numerous industrial applications. The mechanisms that determine the contact angles for such liquids remain poorly understood, with many intricacies arising due to complex physical phenomena, for example, due to the presence of surfactants. Here, we consider two-component drops that consist of mixtures of vicinal alkanediols and water. These diols behave surfactant-like in water. However, the contact angles of such mixtures on solid substrates are surprisingly large. We experimentally reveal that the contact angle is determined by two separate mechanisms of completely different nature, namely, Marangoni contraction (hydrodynamic) and autophobing (molecular). The competition between these effects can even inhibit Marangoni contraction, highlighting the importance of molecular structures in physico-chemical hydrodynamics.

Hansen solubility parameters obtained via molecular dynamics simulations as a route to predict siloxane surfactant adsorption.

HYPOTHESIS: The Hansen Solubility Parameters (HSP) derived from Molecular Dynamics (MD) simulations can be used as a fast approach to predict surfactants adsorption on a solid surface. Experiments and simulations: We focused on the specific case of siloxane-based surfactants adsorption on silicon oxide surface (SiO2), encountered in inkjet printing processes. A simplified atomistic model of the SiO2 surface was designed to enable the computation of its solubility parameter using MD, and to subsequently determine the interactions of the SiO2 surface with the siloxane-based surfactant and the various solvents employed. Surfactant adsorption was characterized experimentally using contact angle goniometry, ellipsometry, XPS and AFM. FINDINGS: Comparison of the numerical results with experiments showed that the HSP theory allows to identify the range of solvents that are likely to prevent surfactant adsorption on the SiO2 surface. The proposed approach indicates that polar solvents, such as acetone and triacetin, which are strongly attracted to the silicon oxide surface might form a shield that prevents siloxane-based surfactants adsorption. This simple approach, can guide the selection of adequate solvents for surfaces and surfactants with specific chemical structures, providing opportunities for controlling interfacial adsorption.

Brush Swelling and Attachment Strength of Barnacle Adhesion Protein on Zwitterionic Polymer Films as a Function of Macromolecular Structure.

The exceptional hydration of sulfobetaine polymer brushes and their resistance toward nonspecific protein absorption allows for the construction of thin films with excellent antibiofouling properties. In this work, swollen sulfobetaine brushes, prepared by surface-initiated atom transfer radical polymerization of two monomers, differentiated by the nature of the polymerizable group, are studied and compared by a liquid-cell atomic force microscopy technique and spectroscopic ellipsometry. Colloidal AFM-based force spectroscopy is employed to estimate brush grafting density and characterize nanomechanical properties in salt water. When the ionic strength-induced swelling behaviors of the two systems are compared, the differences observed on the antipolyelectrolyte response can be correlated with the stiffness variation on brush compression, likely to be promoted by solvation differences. The higher solvation of amide groups is proposed to be responsible for the lower adhesion force of the barnacle cyprid's temporary adhesive proteins. The adhesion results provide further insights into the antibiofouling activity against barnacle cyprid settlement attributed to polysulfobetaine brushes.

Self-assembly and wetting properties of gold nanorod-CTAB molecules on HOPG.

The formation of self-assembled superstructures of cetyltrimethylammonium bromide (CTAB) after drying on a nonwetting highly ordered pyrolytic graphite (HOPG) surface have been investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Although SEM did not reveal coverage of CTAB layers, AFM showed not only CTAB assembly, but also the dynamics of the process on the surface. The self-assembled layers of CTAB molecules on the HOPG terraces prior to nanorod deposition were shown to change the wettability of the surface, and as a result, gold nanorod deposition takes place on nonwetting HOPG terraces.

Tuning the Friction of Graphene on Mica by Alcohol Intercalation.

The friction of graphene on mica was studied using lateral force microscopy. We observed that intercalation of alcohol molecules significantly increases the friction of graphene, as compared to water. An increase of 1.8, 2.4, and 5.9 times in friction between the atomic force microscopy tip and  single-layer graphene was observed for methanol, ethanol, and 2-propanol, respectively. Moreover, the friction of graphene is found to be higher for single-layer graphene than for multilayer graphene. We attribute the increase in friction to the additional vibrational modes of alcohol molecules. The significant variation of the frictional characteristics of graphene at the nanoscale by altering the intercalant could open up applications for the next-generation nanolubricants and nanodevices.

Charge Induced Dynamics of Water in a Graphene-Mica Slit Pore.

We use atomic force microscopy to in situ investigate the dynamic behavior of confined water at the interface between graphene and mica. The graphene is either uncharged, negatively charged, or positively charged. At high humidity, a third water layer will intercalate between graphene and mica. When graphene is negatively charged, the interface fills faster with a complete three layer water film, compared to uncharged graphene. As charged positively, the third water layer dewets the interface, either by evaporation into the ambient or by the formation of three-dimensional droplets under the graphene, on top of the bilayer. Our experimental findings reveal novel phenomena of water at the nanoscale, which are interesting from a fundamental point of view and demonstrate the direct control over the wetting properties of the graphene/water interface.

Electrochemically Induced Nanobubbles between Graphene and Mica.

We present a new method to create dynamic nanobubbles. The nanobubbles are created between graphene and mica by reducing intercalated water to hydrogen. The nanobubbles have a typical radius of several hundred nanometers, a height of a few tens of nanometers and an internal pressure in the range of 0.5-8 MPa. Our approach paves the way to the realization of nanobubbles of which both size and internal pressure are tunable.

Collective and convective effects compete in patterns of dissolving surface droplets.

The effects of neighboring droplets on the dissolution of a sessile droplet, i.e. collective effects, are investigated both experimentally and numerically. On the experimental side small approximately 20 nL mono-disperse surface droplets arranged in an ordered pattern were dissolved and their size evolution is studied optically. The droplet dissolution time was studied for various droplet patterns. On the numerical side, lattice-Boltzmann simulations were performed. Both simulations and experiments show that the dissolution time of a droplet placed in the center of a pattern can increase by as much as 60% as compared to a single, isolated droplet, due to the shielding effect of the neighboring droplets. However, the experiments also show that neighboring droplets enhance the buoyancy driven convective flow of the bulk, increasing the mass exchange and counteracting collective effects. We show that this enhanced convection can reduce the dissolution time of droplets at the edges of the pattern to values below that of a single, isolated droplet.

Structure and Dynamics of Confined Alcohol-Water Mixtures.

The effect of confinement between mica and graphene on the structure and dynamics of alcohol-water mixtures has been studied in situ and in real time at the molecular level by atomic force microscopy (AFM) at room temperature. AFM images reveal that the adsorbed molecules are segregated into faceted alcohol-rich islands on top of an ice layer on mica, surrounded by a pre-existing multilayer water-rich film. These faceted islands are in direct contact with the graphene surface, revealing a preferred adsorption site. Moreover, alcohol adsorption at low relative humidity (RH) reveals a strong preference of the alcohol molecules for the ordered ice interface. The growth dynamics of the alcohol islands is governed by supersaturation, temperature, the free energy of attachment of molecules to the island edge and two-dimensional (2D) diffusion. The measured diffusion coefficients display a size dependence on the molecular size of the alcohols, and are about 6 orders of magnitude smaller than the bulk diffusion coefficients, demonstrating the effect of confinement on the behavior of the alcohols. These experimental results provide new insights into the behavior of multicomponent fluids in confined geometries, which is of paramount importance in nanofluidics and biology.

Hydrodynamic confinement and capillary alignment of gold nanorods.

Controlling the alignment and orientation of nanorods on various surfaces poses major challenges. In this work, we investigate hydrodynamic confinement and capillary alignment of gold nanorod assembly on chemically stripe-patterned substrates. The surface patterns consist of alternating hydrophilic and hydrophobic micrometer wide stripes; a macroscopic wettability gradient enables controlling the dynamics of deposited suspension droplets. We show that drying of residual liquid on the hydrophilic stripes gives rise to spatially localized deposition and alignment of the nanorods. Moreover, a universal relation between the extent of order within the single layers of nanoparticles and the lateral dimension of the deposits is presented and discussed.

Optical Response of Silver Nanoneedles on a Mirror.

Plasmonic properties of metal nanostructures are appealing due to their potential to enhance photovoltaics or sensing performance. Our aim was to identify the plasmonic characteristics of silver nanoneedles on a reflective layer in the polarized optical response. Experimental ellipsometry results are complemented by finite-difference time-domain (FDTD) calculations. Plasmon resonances on the nanoneedles can indeed be observed in the polarized optical response. This study reveals the details of the complex antenna-like behaviour of the nanoneedles which gives an agreement between experiment and FDTD simulation. The simulations show that the plasmon resonances lead to an effective negative refractive index, originating from the negative refractive index of the nanoneedles in combination with its supporting substrate, i.e. a mirror. This original study of a complex plasmonic system by ellipsometry and FDTD has great relevance for applications, making use of intricate light matter interaction.

Closed-loop conductance scanning tunneling spectroscopy: demonstrating the equivalence to the open-loop alternative.

We demonstrate the validity of using closed-loop z(V) conductance scanning tunneling spectroscopy (STS) measurements for the determination of the effective tunneling barrier by comparing them to more conventional open-loop I(z) measurements. Through the development of a numerical model, the individual contributions to the effective tunneling barrier present in these experiments, such as the work function and the presence of an image charge, are determined quantitatively. This opens up the possibility of determining tunneling barriers of both vacuum and molecular systems in an alternative and more detailed manner.

Latent heat induced rotation limited aggregation in 2D ice nanocrystals.

The basic science responsible for the fascinating shapes of ice crystals and snowflakes is still not understood. Insufficient knowledge of the interaction potentials and the lack of relevant experimental access to the growth process are to blame for this failure. Here, we study the growth of fractal nanostructures in a two-dimensional (2D) system, intercalated between mica and graphene. Based on our scanning tunneling spectroscopy data, we provide compelling evidence that these fractals are 2D ice. They grow while they are in material contact with the atmosphere at 20 °C and without significant thermal contact to the ambient. The growth is studied in situ, in real time and space at the nanoscale. We find that the growing 2D ice nanocrystals assume a fractal shape, which is conventionally attributed to Diffusion Limited Aggregation (DLA). However, DLA requires a low mass density mother phase, in contrast to the actual currently present high mass density mother phase. Latent heat effects and consequent transport of heat and molecules are found to be key ingredients for understanding the evolution of the snow (ice) flakes. We conclude that not the local availability of water molecules (DLA), but rather them having the locally required orientation is the key factor for incorporation into the 2D ice nanocrystal. In combination with the transport of latent heat, we attribute the evolution of fractal 2D ice nanocrystals to local temperature dependent rotation limited aggregation. The ice growth occurs under extreme supersaturation, i.e., the conditions closely resemble the natural ones for the growth of complex 2D snow (ice) flakes and we consider our findings crucial for solving the "perennial" snow (ice) flake enigma.

Stick-jump mode in surface droplet dissolution.

The analogy between evaporating surface droplets in air to dissolving long-chain alcohol droplets in water is worked out. We show that next to the three known modi for surface droplet evaporation or dissolution (constant contact angle mode, constant contact radius mode, and stick-slide mode), a fourth mode exists for small droplets on supposedly smooth substrates, the stick-jump mode: intermittent contact line pinning causes the droplet to switch between sticking and jumping during the dissolution. We present experimental data and compare them to theory to predict the dissolution time in this stick-jump mode. We also explain why these jumps were easily observed for microscale droplets but not for larger droplets.

Evaporative gold nanorod assembly on chemically stripe-patterned gradient surfaces.

Experimentally we explore the potential of using pre-defined motion of a receding contact line to control the deposition of nanoparticles from suspension. Stripe-patterned wettability gradients are employed, which consist of alternating hydrophilic and hydrophobic stripes with increasing macroscopic surface energy. Nanoparticle suspensions containing nanorods and nanospheres are deposited onto these substrates and left to dry. After moving over the pattern and evaporation of the solvent, characteristic nanoparticle deposits are found. The liquid dynamics has a pronounced effect on the spatial distribution. Nanoparticles do not deposit on the hydrophobic regions; there is high preference to deposit on the wetting stripes. Moreover, the fact that distributed nanoparticle islands are formed suggests that the receding of the contact line occurs in a stick-slip like fashion. Furthermore, the formation of liquid bridges covering multiple stripes during motion of the droplet over the patterns is modeled. We discuss their origin and show that the residue after drying, containing both nanoparticles and the stabilizing surfactant, also resembles such dynamics. Finally, zooming into individual islands reveals that highly selective phase separation occurs based on size and shape of the nanoparticles.

Water-induced blister formation in a thin film polymer.

A failure mechanism of thin film polymers immersed in water is presented: the formation of blisters. The growth of blisters is counterintuitive as the substrates were noncorroding and the polymer does not swell in water. We identify osmosis as the driving force behind the blister formation. The dynamics of the blister formation is studied experimentally as well as theoretically, and a quantitative model describing the blister growth is developed, which accurately describes the temporal evolution of the blisters.

Shape of picoliter droplets on chemically striped patterned substrates.

We studied the shape of water droplets deposited using an inkjet nozzle on a chemically striped patterned substrate consisting of alternating hydrophobic and hydrophilic stripes. The droplet dimensions are comparable to the period of the stripes, typically covering up to 13 stripes. As such, our present results bridge the gap linking two regimes previously considered: (i) droplets on single stripes and (ii) droplets covering more than 50 stripes. In line with previous work on markedly smaller water droplets, the exact deposition position is important for the final shape of the droplets. A droplet with its center deposited on a hydrophobic stripe reaches a shape that is different than when it is deposited on a hydrophilic stripe. Experimental results of different droplet configurations on the same surface are in agreement with simulations using the lattice Boltzmann model. In addition, the simulations enable a detailed analysis of droplet free energies and the volume dependence. The latter reveals scaling properties of shape parameters in terms of droplet radius scaled to the period of the stripe pattern, which have remained unexplored until now.

Exposing nanobubble-like objects to a degassed environment.

The primary attribute of interest of surface nanobubbles is their unusual stability and a number of theories trying to explain this have been put forward. Interestingly, the dissolution of nanobubbles is a topic that did not receive a lot of attention yet. In this work we applied two different experimental procedures which should cause gaseous nanobubbles to completely dissolve. In our experiments we nucleated nanobubble-like objects by putting a drop of water on HOPG using a plastic syringe and a disposable needle. In method A, the nanobubble-like objects were exposed to a flow of degassed water (1.17 mg l(-1)) for 96 hours. In method B, the ambient pressure was lowered in order to degas the liquid and the nanobubble-like objects. Interestingly, the nanobubble-like objects remained stable after exposure to both methods. After thorough investigation of the procedures and materials used during our experiments, we found that the nanobubble-like objects were induced by the use of disposable needles in which PDMS contaminated the water. It is very important for the nanobubble community to be aware of the fact that, although features look and behave like nanobubbles, in some cases they might in fact be induced by contamination. The presence of contamination could also resolve some inconsistencies found in the nanobubble literature.