Electrical Chain Rearrangement: What Happens When Polymers in Brushes Have a Charge Gradient?

Under the influence of electric fields, the chains in polyelectrolyte brushes can stretch and collapse, which changes the structure of the brush. Copolymer brushes with charged and uncharged monomers display a similar behavior. For pure polyelectrolyte and random copolymer brushes, the field-induced structure changes only the density of the brush and not its local composition, while the latter could be affected if charges are distributed inhomogeneously along the polymer backbone. Therefore, we systematically study the switching behavior of gradient polyelectrolyte brushes in electric fields for different solvent qualities, grafting densities, and charges per chain via coarse-grained molecular dynamics simulations. Similar to random copolymers and pure polyelectrolytes, these brushes show a mixed-phase transition: intermediate states between fully stretched and collapsed are characterized by a bimodal chain-end distribution. Additionally, we find that the total charge of the brush plays a key role in the critical field required for a complete transition. Finally, we find that gradient polyelectrolyte brushes are charge-enriched at the brush-solvent interface under stretched conditions and charge-depleted under collapsed conditions, allowing for control over the local composition and thus the surface charge of the brush due to the inhomogeneous charge along the grafted chains.

On the Road to Circular Polymer Brushes: Challenges and Prospects.

Polymer brushes are unique surface coatings that have been of high interest in research for the past decades due to their covalent tethering to surfaces and the broad spectrum of polymers that can be grafted to or grafted from various surfaces. Modification of surfaces with brushes may provide lubricious and/or antifouling properties, and they can also potentially be used in many application fields due to their high responsiveness toward certain stimuli. Generally, polymer brushes are long-lasting coatings, while their end-of-life has to date largely been neglected. Therefore, it is important to consider additional design methodologies to produce circular brushes, which will degrade after a certain period of time such that surfaces can be reused, and the potentially obtained monomers may be used again to synthesize new brushes. In this Perspective, we aim to tackle and understand the challenges to translate the knowledge on degradation and chemical recycling of bulk polymers toward circular polymer brushes. We summarized the recent developments on (bio)degradable polymer brushes and the challenges that are to be tackled toward their potential implementation as circular coatings.

Pressure Anisotropy in Polymer Brushes and Its Effects on Wetting.

Polymer brushes, coatings consisting of densely grafted macromolecules, experience an intrinsic lateral compressive pressure, originating from chain elasticity and excluded volume interactions. This lateral pressure complicates a proper definition of the interface and, thereby, the determination and interpretation of the interfacial tension and its relation to the wetting behavior of brushes. Here, we study the link among grafting-induced compressive lateral pressure in polymer brushes, interfacial tension, and brush wettability using coarse-grained molecular dynamics simulations. We focus on grafting densities and polymer-liquid affinities such that the polymer and liquid do not tend to mix. For these systems, a central result is that the liquid contact angle is independent of the grafting density, which implies that the grafting-induced lateral compressive pressure in the brush does not influence its wettability. Although the definition of brush interfacial tensions is complicated by the grafting-induced pressure, the difference in the interfacial tension between wet and dry brushes is perfectly well-defined. We confirm explicitly from Young's law that this difference offers an accurate description of the brush wettability. We then explore a method to isolate the grafting-induced contribution to the lateral pressure, assuming the interfacial tension is independent of grafting density. This scenario indeed allows disentanglement of interfacial and grafting effects for a broad range of parameters, except close to the mixing point. We separately discuss the latter case in light of autophobic dewetting.

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.

Carbon monoxide separation: past, present and future.

Large amounts of carbon monoxide are produced by industrial processes such as biomass gasification and steel manufacturing. The CO present in vent streams is often burnt, this produces a large amount of CO2, e.g., oxidation of CO from metallurgic flue gasses is solely responsible for 2.7% of manmade CO2 emissions. The separation of N2 from CO due to their very similar physical properties is very challenging, meaning that numerous energy-intensive steps are required for CO separation, making the CO separation from many process streams uneconomical in spite of CO being a valuable building block in the production of major chemicals through C1 chemistry and the production of linear hydrocarbons by the Fischer-Tropsch process. The development of suitable processes for the separation of carbon monoxide has both industrial and environmental significance. Especially since CO is a main product of electrocatalytic CO2 reduction, an emerging sustainable technology to enable carbon neutrality. This technology also requires an energy-efficient separation process. Therefore, there is a great need to develop energy efficient CO separation processes adequate for these different process streams. As such the urgency of separating carbon monoxide is gaining greater recognition, with research in the field becoming more and more crucial. This review details the principles on which CO separation is based and provides an overview of currently commercialised CO separation processes and their limitations. Adsorption is identified as a technology with the potential for CO separation with high selectivity and energy efficiency. We review the research efforts, mainly seen in the last decades, in developing new materials for CO separation via ad/bsorption and membrane technology. We have geared our review to both traditional CO sources and emerging CO sources, including CO production from CO2 conversion. To that end, a variety of emerging processes as potential CO2-to-CO technologies are discussed and, specifically, the need for CO capture after electrochemical CO2 reduction is highlighted, which is still underexposed in the available literature. Altogether, we aim to highlight the knowledge gaps that could guide future research to improve CO separation performance for industrial implementation.

Electrostatic Fields Stimulate Absorption of Small Neutral Molecules in Gradient Polyelectrolyte Brushes.

Molecules can partition from a solution into a polymer coating, leading to a local enrichment. If one can control this enrichment via external stimuli, one can implement such coatings in novel separation technologies. Unfortunately, these coatings are often resource intensive as they require stimuli in the form changes of bulk solvent conditions such as acidity, temperature, or ionic strength. Electrically driven separation technology may provide an appealing alternative, as this will allow local, surface-bound stimuli instead of system-wide bulk stimuli to induce responsiveness. Therefore, we investigate via coarse grained molecular dynamics simulations the possibility of using coatings with charged moieties, specifically gradient polyelectrolyte brushes, to control the enrichment of the neutral target molecules near the surface with applied electric fields. We find that targets which interact more strongly with the brush show both more absorption and a larger modulation by electric fields. For the strongest interactions evaluated in this work, we obtained absorption changes of over 300 % between the collapsed and extended state of the coating.

Nonequilibrium configurations of swelling polymer brush layers induced by spreading drops of weakly volatile oil.

Polymer brush layers are responsive materials that swell in contact with good solvents and their vapors. We deposit drops of an almost completely wetting volatile oil onto an oleophilic polymer brush layer and follow the response of the system upon simultaneous exposure to both liquid and vapor. Interferometric imaging shows that a halo of partly swollen polymer brush layer forms ahead of the moving contact line. The swelling dynamics of this halo is controlled by a subtle balance of direct imbibition from the drop into the brush layer and vapor phase transport and can lead to very long-lived transient swelling profiles as well as nonequilibrium configurations involving thickness gradients in a stationary state. A gradient dynamics model based on a free energy functional with three coupled fields is developed and numerically solved. It describes experimental observations and reveals how local evaporation and condensation conspire to stabilize the inhomogeneous nonequilibrium stationary swelling profiles. A quantitative comparison of experiments and calculations provides access to the solvent diffusion coefficient within the brush layer. Overall, the results highlight the-presumably generally applicable-crucial role of vapor phase transport in dynamic wetting phenomena involving volatile liquids on swelling functional surfaces.

Vapor Swelling of Polymer Brushes Compared to Nongrafted Films.

Polymer brushes, coatings of polymers covalently end-grafted to a surface, have been proposed as a more stable alternative to traditional physisorbed coatings. However, when such coatings are applied in settings such as vapor sensing and gas separation technologies, their responsiveness to solvent vapors becomes an important consideration. It can be anticipated that the end-anchoring in polymer brushes reduces the translational entropy of the polymers and instead introduces an entropic penalty against stretching when vapor is absorbed. Therefore, swelling can be expected to be diminished in brushes compared to nongrafted films. Here, we study the effect of the anchoring-constraint on vapor sorption in polymer coatings using coarse-grained molecular dynamics simulations as well as humidity-controlled ellipsometry on chemically identical polymer brushes and nongrafted films. We find a qualitative agreement between simulations and experiments, with both indicating that brushes certainly swell less than physisorbed films, although this effect is minor for common grafting densities. Our results imply that polymer brushes indeed hold great potential for the intended applications.

Enhanced vapor sorption in block and random copolymer brushes.

Polymer brushes in gaseous environments absorb and adsorb vapors of favorable solvents, which makes them potentially relevant for sensing applications and separation technologies. Though significant amounts of vapor are sorbed in homopolymer brushes at high vapor pressures, at low vapor pressures sorption remains limited. In this work, we vary the structure of two-component polymer brushes and investigate the enhancement in vapor sorption at different relative vapor pressures compared to homopolymer brushes. We perform molecular dynamics simulations on two-component block and random copolymer brushes and investigate the influence of monomer miscibility and formation of high-energy interfaces between immiscible monomers on vapor sorption. Additionally, we present absorption isotherms of pure homopolymer, mixed binary brush and 2-block, 4-block, and random copolymer brushes. Based on these isotherms, we finally show that random copolymer brushes absorb more vapor than any other architecture investigated thus far. Random brushes display enhanced sorption at both high and low vapor pressures, with the largest enhancement in sorption at low vapor pressures.

Chemical Composition and Strain at Interfaces between Different Morphologies in Block Copolymer Thin Films.

Transitional composition between two thin-film morphologies of the block copolymer, polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBuA), was investigated using near-field infrared spectroscopy and atomic force microscopy mechanical measurements. These techniques allowed block identification with nanoscale spatial resolution and elucidated the material's sub-surface composition. PS was found to form coronae around the PtBuA block in spherical valleys on flat areas of the film, and coronae of PtBuA surrounding the PS lamellae were observed at the edge of the polymer film, where parallel lamellae are formed. Furthermore, we found that the peak position and width varied by location, which may be a result of block composition, chain tension, or substrate interaction.

The role of entropy in wetting of polymer brushes.

The wetting of polymer brushes exhibits a much richer phenomenology than wetting of normal solid substrates. These brushes allow for three wetting states, which are partial wetting, complete wetting and mixing. Here, we study the transitions between these wetting states for brushes in contact with polymer melts and compare them to predictions using enthalpic arguments based on brush and melt interactions. We show that the transitions are shifted compared to the enthalpic predictions and that the shifts can be positive or negative depending on the length of the melt polymer and the brush grafting density. The reason for this is that these brush and melt parameters can have a positive or negative effect on the entropic contribution to the free energy of the system. Our results highlight the relevance of entropy in predicting the exact wetting transitions, which is important for the design of brush-based coating applications.

Autonomous capillary microfluidic devices with constant flow rate and temperature-controlled valving.

In this paper, we report on a capillary microfluidic device with constant flow rate and temperature-triggered stop valve function. It contains a PDMS channel that was grafted by a thermo-responsive polymer poly(N-isopropylacrylamide) (PNIPAm). The channel exhibits a constant capillary filling speed. By locally increasing the temperature in the channel from 20 °C to 37 °C using a microfabricated heater, a change of the surface wettability from hydrophilic to hydrophobic is obtained creating a hydrophobic stop valve. The valve can be reopened by lowering the temperature. The device is simple to fabricate and can be used as an actuatable capillary pump operating around room temperature. To understand the constant capillary filling speed, we performed contact angle measurements, in which we found slow wetting kinetics of PNIPAm-g-PDMS surfaces at temperatures below the lower critical solution temperature (LCST) of PNIPAm and fast wetting kinetics above the LCST. We interpret this as the result of the diffusive hydration process of PNIPAm below the LCST and the absence of hydration on the hydrophobic PNIPAm thin layer above the LCST.

Design, construction, and testing of an accurate low-cost humidistat for laboratory-scale applications.

Stable and precise control of humidity is imperative for a wide variety of experiments. However, commercially available humidistats (devices that maintain a constant humidity) are often prohibitively expensive. Here, we present a simple yet effective humidistat for laboratory-scale applications that can be easily and affordably (<€250) constructed based on an Arduino Uno as microcontroller, a set of proportional miniature solenoid valves, a gas washing bottle, and a humidity sensor. The microcontroller implements a PID controller that regulates the ratio of a dry and humid airflow. The design and implementation of the device, including a custom driver circuit for the solenoids, are described in detail, and the firmware is freely available online. Finally, we demonstrate its proper operation and performance through step response and long-term stability tests, which shows settling times of approx. 30 s and an attainable relative humidity range of 10-95.

Vapor sorption in binary polymer brushes: The effect of the polymer-polymer interface.

Polymer brushes attract vapors that are good solvents for polymers. This is useful in sensing and other technologies that rely on concentrating vapors for optimal performance. It was recently shown that vapor sorption can be enhanced further by incorporating two incompatible types of polymers A and B in the brushes: additional vapor adsorbs at the high-energy polymer-polymer interface in these binary brushes. In this article, we present a model that describes this enhanced sorption in binary brushes of immiscible A-B polymers. To do so, we set up a free-energy model to predict the interfacial area between the different polymer phases in binary brushes. This description is combined with Gibbs adsorption isotherms to determine the adsorption at these interfaces. We validate our model with coarse-grained molecular dynamics simulations. Moreover, based on our results, we propose design parameters (A-B chain fraction, grafting density, vapor, and A-B interaction strength) for optimal vapor absorption in coatings composed of binary brushes.

Swelling of Poly(methyl acrylate) Brushes in Acetone Vapor.

Sensor platforms can benefit from the incorporation of polymer brushes since brushes can concentrate the analyte near the sensor surface. Brushes that absorb acetone vapor are of particular interest since acetone is an important marker for biological processes. We present a simple procedure to synthesize acetone-responsive poly(methyl acrylate) brushes. Using spectroscopic ellipsometry, we show that these brushes respond within seconds and swell by more than 30% when exposed to acetone vapor. Moreover, quartz crystal microbalance measurements demonstrate that the brushes can be exploited to increase the acetone detection sensitivity of sensors by more than a factor 6. Surprisingly, we find that the swelling ratio of the brushes in acetone vapor is independent of the grafting density and the degree of polymerization of the polymers in the brush. This is qualitatively different from swelling of the same brushes in liquid environments, where the swelling ratio decreases for increasing grafting densities. Yet, it indicates that the brushes are robust and reproducible candidates for implementation in vapor sensor systems.

Redox-Induced Backbiting of Surface-Tethered Alkylsulfonate Amphiphiles: Reversible Switching of Surface Wettability and Adherence.

The synthesis and characterization of electrode-supported poly(ferrocenylsilane) (PFS) films bearing iodopropyl (PFS-I) and undecanesulfonate (PFS-SO3(-)) surface moieties are presented. The redox responsiveness of these PFS films allows for controlled and repeatable switching of the surface energy of the PFS-I and PFS-SO3(-) layers under electrochemical control. Static water/surface contact angle measurements showed a change in contact angle values for PFS-I from 80° (reduced state) to 70° (oxidized state) over repeated cycles. However, an opposite change in wettability was observed for PFS-SO3(-), where the values observed varied from 59° (reduced state) to 77° (oxidized state). Nanoscale adherence was assessed with colloid probe AFM. The adhesive forces between these surfaces and a polystyrene (PS) colloid probe in water alternated between 130 nN (reduced state) and 30 nN (oxidized state) for PFS-I layers and between 75 nN (reduced) and 180 nN (oxidized) for the PFS-SO3(-) films. The reversed response of PFS-I films to oxidation compared to that of PFS-SO3(-), in both contact angles and adhesive forces, suggests a different underlying mechanism for switching. As PFS-I is tuned from the reduced to the oxidized state, positively charged ferrocenium (Fc(+)) centers that formed in the film increase its wettability and reduce its adherence to the hydrophobic colloid probe. For PFS-SO3(-) in the reduced state, the exposed alkanesulfonate moieties increase the hydrophilicity of the surface. When oxidized, the Fc(+) units attract the negatively charged sulfonate groups, which results in a bending of the sulfonate groups toward the PFS surface, exposing the undecyl spacer. This alteration of the surface chemistry reduces the surface energy and increases the adherence between the bent alkyl chains and the hydrophobic PS colloid in water. The attraction of the charged sulfonate group to Fc(+) is in competition with the counterions present in the electrolyte solution. Therefore, the backbiting of the chain can be achieved only in electrolytes where the affinity of Fc(+) for the ions is lower than for the sulfonate group, in agreement with the Hofmeister series.

Stretching of collapsed polymers causes an enhanced dissipative response of PNIPAM brushes near their LCST.

Poly(N-isopropyl acrylamide) (PNIPAM) is a stimulus-responsive polymer that can switch in water from an expanded state below the lower critical solution temperature (LCST) of 32 °C to a globular state above the LCST. It was recently shown that, as a consequence of this conformational transition, the interfacial and (tribo-)mechanical properties of polymeric systems composed of PNIPAM can be switched between two states. Here we show that the tribo-mechanical properties of a particular type of PNIPAM system, which is the PNIPAM brush, do not just change between two states, but instead evolve continuously and non-monotonically upon increasing/decreasing temperature. To do so, we present atomic force microscopy experiments in which we measure the adhesion hysteresis and the friction upon bringing a gold colloid in relative motion with PNIPAM brushes at temperatures around the LCST. Both the friction and the adhesion hysteresis display a pronounced maximum exactly at the LCST. The force vs. distance data captured at these temperatures show a long-ranged adhesive interaction upon moving the colloid away from the original point of contact, which indicates that during this retraction the partly collapsed polymers in the brush become strongly stretched.

Switchable friction using contacts of stimulus-responsive and nonresponding swollen polymer brushes.

Stimulus-responsive (SR), solvated polymers can switch between an expanded state and a collapsed state via external stimuli. Using molecular dynamics simulations, I show that such SR polymers can be employed to control the frictional response between two opposing polymer brushes in relative sliding motion. By using a brush composed of SR polymers in contact with a nonresponding solvated polymer brush, the presence of capillaries and the overlap between molecules of the opposing brushes can be switched. When both brushes are solvated, a capillary is formed and polymers of the opposing brushes interdigitate. Interdigitation dominates friction upon shearing flat brush-bearing surfaces, while the breaking and formation of capillaries dominate friction in the low-velocity limit between rough brush-bearing surfaces. Thus, when either rough or flat polymer-bearing surfaces are sheared, friction between two swollen brushes can be high. In contrast, when the SR brush is collapsed, the solvent absorbs only in the brush that does not respond to the external stimulus. The latter circumvents the presence of capillaries and interdigitation of the brushes, which results in a low friction force upon shearing.

PNIPAM Brushes in Colloidal Photonic Crystals Enable Ex Situ Ethanol Vapor Sensing.

Structural colors are formed by the periodic repetition of nanostructures in a material. Upon reversibly tuning the size or optical properties of the repetitive unit inside a nanostructured material, responsive materials can be made that change color due to external stimuli. This paper presents a simple method to obtain films of ethanol vapor-responsive structural colors based on stacked poly(N-isopropylacrylamide) (PNIPAM)-grafted silica nanoparticles. Our materials show clear, reversible color transitions in the presence of near-saturated ethanol vapor. Moreover, due to the absorption of ethanol in the PNIPAM brushes, relatively long recovery times are observed (∼30 s). Materials based on bare or poly(methyl methacrylate) (PMMA) brush-grafted silica nanoparticles also change color in the presence of ethanol vapor but possess significantly shorter recovery times (∼1 s). Atomic force microscopy reveals that the delayed recovery originates from the ability of PNIPAM brushes to swell in ethanol vapor. This renders the films highly suitable for ex situ ethanol vapor sensing.