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We explore the effect of poly (ethylene glycol) (PEG) molar mass on the intrinsic permeability and structural characteristics of poly (ethylene glycol) diacrylate PEGDA/PEG composite hydrogel membranes. We observe that by varying the PEG content and molar mass, we can finely adjust the water intrinsic permeability over several orders of magnitude. Notably, we show the existence of a maximum water intrinsic permeability, already identified in a previous study to be located at the critical overlap concentration C^* of PEG chains, for the highest PEG molar mass studied. Furthermore, we note that the maximum intrinsic permeability follows a non-monotonic evolution with respect to the PEG molar mass and reaches its peak at 35 000 g.mol-1. Besides our results show that a significant fraction of PEG chains is irreversibly trapped within the PEGDA matrix even for the shortest molar masses down to 600 g.mol-1. This observation suggests the possibility of covalent grafting of PEG chains to the PEGDA matrix. CryoSEM and AFM measurements demonstrate the presence of large micron-sized cavities separated by PEGDA-rich walls whose nanometric structure strongly depends on the PEG content. By combining our permeability and structural measurements, we suggest that the PEG chains trapped inside the PEGDA rich walls induce nanoscale defects in the cross linking density, resulting in an increased permeability below C^*. Conversely, above C^*, we speculate that partially-trapped PEG chains may form a brush-like arrangement on the surface of the PEGDA-rich walls, leading to a reduction in permeability. These two opposing effects are anticipated to exhibit molar-mass-dependent trends, contributing to the non-monotonic variation of the maximum intrinsic permeability at C^*. Overall, our results demonstrate the potential to fine-tune the properties of hydrogel membranes, offering new opportunities in separation applications.

Polymer association at liquid-liquid interfaces is a promising way to spontaneously obtain soft self-healing membranes. In the case of reversible bonding between two polymers, the macromolecules are mobile everywhere within the membrane and they can be absorbed into it at both boundaries due to binding to macromolecules of the other type. In this work, we develop the theoretical model of membrane growth based on these assumptions. The asymptotic dependence of membrane thickness on time as h ~ t^(1/2), as typically observed in experiments in a stationary regime, reveals an interdiffusion-controlled process, where the polymer fluxes sustain the polymer absorption at the membrane boundaries. The membrane growth rate is mainly determined by the difference in equilibrium compositions at the boundaries, the association constant, the polymer lengths and mobilities. This model is further used to describe the growth of hydrogel membranes formed via H-bonding of polymers at the interface between a solution of poly(propylene oxide) (PPO) in isopropyl myristate and an aqueous solution of poly(methacrylic acid) (PMAA). The film thickness is measured by reflectometric methods. The dependence of thickness on time can be approximated by the power law t^(beta), where beta= 1/2 for the PMAA solution at pH=3 and decreases with increasing pH and, hence, ionization degree. The growth rate slows down about 25 times for 500-nm-thick films at pH = 5.1 compared to the case of pH = 3. The ionization degree of PMAA solutions was studied by potentiometric methods. Even a small change in ionization was found to influence the growth rate of the film. A slowdown of the film growth for the ionized polymer can be explained by a drop in the composition gradient in the membrane, as is predicted by the proposed model.

Hydrogels are promising systems for separation applications due to their structural characteristics (i.e. hydrophilicity and porosity). In our study, we investigate the permeation of suspensions of rigid latex particles of different sizes through free-standing hydrogel membranes prepared by photopolymerization of a mixture of poly (ethylene glycol) diacrylate (PEGDA) and large poly (ethylene glycol) (PEG) chains of 300 000 g.mol-1 in the presence of a photoinitiator. Atomic force microscopy (AFM) and cryoscanning electron microscopy (cryoSEM) were employed to characterize the structure of the hydrogel membranes. We find that the 20 nm particle permeation depends on both the PEGDA/PEG composition and the pressure applied during filtration. In contrast, we do not measure a significant permeation of the 100 nm and 1 $\mu$m particles, despite the presence of large cavities of 1 $\mu$m evidenced by cryoSEM images. We suggest that the PEG chains induce local nanoscale defects in the cross-linking of PEGDA-rich walls separating the micron size cavities, that control the permeation of particles and water. Moreover, we discuss the decline of the permeation flux observed in the presence of latex particles, compared to that of pure water. We suggest that a thin layer of particles forms on the surface of the hydrogels.

Hydrogels which are hydrophilic and porous materials have recently emerged as promising systems for filtration applications. In our study, we prepare hydrogel membranes by the photopolymerization of a mixture of poly (ethylene glycol) diacrylate (PEGDA) and large poly(ethylene glycol) (PEG) chains of 300 000 g.mol-1 in the presence of a photoinitiator. We find that this addition of free PEG chains induces a large and non-linear increase of the water permeability. Indeed, by changing the content of PEG chains added, we obtain variations of the hydrogel water permeability over two orders of magnitude. The highest water permeability values are obtained for the membranes when the PEG concentration is equal to its critical overlap concentration C*. Moreover, we find that the flow rate of water through the membranes varies non-linearly with the pressure. We relate this result to the deformability of the membranes as the applied pressure leads to a compression of the pores. This study provides new perspectives for the design of flexible hydrogel membranes with controlled permeability and their application in water treatment and bioseparation.

Complexation of polymers at liquid interfaces is an emerging technique to produce all-liquid printable and self-healing devices and membranes. It is crucial to control the assembly process but the mechanisms at play remain unclear. Using two different reflectometric methods, we investigate the spontaneous growth of H-bonded PPO-PMAA membranes at a flat liquid-liquid interface. We find that the membrane thickness h grows with time t as h~t^(1/2), which is reminiscent of a diffusion-limited process. However, counter-intuitively, we observe that this process is faster as the PPO molar mass increases. We are able to rationalize these results with a model which considers the diffusion of the PPO chains within the growing membrane. The architecture of the latter is described as a gel-like porous network, with a pore size much smaller than the radius of the diffusing PPO chains, thus inducing entropic barriers that hinder the diffusion process. From the comparison between the experimental data and the result of the model, we extract some key piece of information about the microscopic structure of the membrane. This study opens the route toward the rational design of self-assembled membranes and capsules with optimal properties.

Hydrophobically modified polymers are good candidates for the stabilization of liquid interfaces thanks to the high anchoring energy of the hydrophobic parts. In this article we probe the interfacial anchoring of a series of home-made hydrophobically modified polymers of controlled degree of grafting by studying their behavior upon large area dilations and compressions. By comparing the measured interfacial tension to the one that we expect in the case of a constant number of adsorbed monomers, we are able to deduce whether desorption or adsorption occurs during area variations. We find that the polymer chains with the longest hydrophobic grafts desorb for larger compressions than the polymers with the shortest grafts, because of their larger desorption energy. Furthermore, we observe more desorption for polymers with the highest grafting densities. We attribute this counter intuitive result to the fact that for high grafting densities, the length of the polymer loops is shorter, hence the elastic penalty upon compression is larger for these layers, leading to a faster desorption. The dilatation experiments reveal that the number of adsorbed anchors remains constant in the case of chains with low grafting density while chains with the highest degree of grafting seem to show some degree of adsorption during the dilatation. Therefore for these highly grafted chains there may be unadsorbed grafts remaining in the vicinity of the interface, which may adsorb quickly to the interface upon dilatation.