Microgels composed of stimuli responsive polymers have attracted worthwhile interest as model colloids for theorethical and experimental studies and for nanotechnological applications. A deep knowledge of their behaviour is fundamental for the design of new materials. Here we report the current understanding of a dual responsive microgel composed of poly(N-isopropylacrylamide) (PNIPAM), a temperature sensitive polymer, and poly(acrylic acid) (PAAc), a pH sensitive polymer, at different temperatures, PAAc contents, concentrations, solvents and pH. The combination of multiple techniques as Dynamic Light Scattering (DLS), Raman spectroscopy, Small Angle Neutron Scattering (SANS), rheology and electrophoretic measurements allow to investigate the hydrodynamic radius behaviour across the typical Volume Phase Transition (VPT), the involved molecular mechanism and the internal particle structure together with the viscoelastic properties and the role of ionic charge in the aggregation phenomena.

Gellan gum-based systems have gained significant attention due to their versatility for multiple applications. In particular, they have shown a great potentiality in the field of cultural heritage, as efficient paper artwork cleaning agents in restoration processes. This efficacy is enhanced when gellan gum is assembled to form stable microgels, by controlling the gelation process under shear. Moreover, the use of methacrylated gellan gum provides additional functionality to the systems, that are also able to remove hydrophobic residues during the cleaning process. However, in order to optimize the manufacturing process, it is fundamental to obtain a thorough understanding of the rheological behaviour of the employed gellan gels in the optimal working conditions for paper cleaning. The present work aims to thoroughly characterize the rheological properties of low-acyl gellan gum, also during hydrogel and microgel formation, assessing the role of temperature (25-80 °C), gellan concentration (0.5-5 % for hydrogels and 0.1-0.5 % for microgels), methacrylation, presence of different cations (Na⁺, Ca²⁺) and salt concentration (0.25-5.0 mM for hydrogels and 100 mM for microgels), on the behaviour of viscosity and viscoelastic moduli. We find the notable result that gellan hydrogels and microgels exhibit a double yielding behaviour in the conditions where they are mostly efficient for art restoration. Furthermore, we identify the optimal rheological conditions of these gels for efficient artwork restoration, opening the possibility to extend their applications to different substrates and in other fields.

Among hydrocolloids, gellan is one of the most studied polysaccharides due to its ability to form mechanically stable gels. Despite its long-standing use, the gellan aggregation mechanism is still not understood because of the lack of atomistic information. Here, we fill this gap by developing a new gellan force field. Our simulations offer the first microscopic overview of gellan aggregation, detecting the coil to single-helix transition at dilute conditions and the formation of higher-order aggregates at high concentration through a two-step process: first, the formation of double helices and then their assembly into superstructures. For both steps, we also assess the role of monovalent and divalent cations, complementing simulations with rheology and atomic force microscopy experiments and highlighting the leading role of divalent cations. These results pave the way for future use of gellan-based systems in a variety of applications, from food science to art restoration.

The phase behaviour of soft colloids has attracted great attention due to the large variety of new phenomenologies emerging from their ability to pack at very high volume fractions. Here we report rheological measurements on interpenetrated polymer network microgels composed of poly(N-isopropylacrylamide) (PNIPAM) and polyacrylic acid (PAAc) at fixed PAAc content as a function of weight concentration. We found three different rheological regimes characteristic of three different states: a Newtonian shear-thinning fluid, an attractive glass characterized by a yield stress, and a jamming state. We discuss the possible molecular mechanisms driving the formation of these states.

Interpenetrated polymer network microgels, composed of crosslinked networks of poly(N-isopropylacrylamide) and polyacrylic acid (PAAc), have been investigated through rheological measurements at four different amounts of PAAc. Both PAAc content and crosslinking degree modify particle dimensions, mass and softness, thereby strongly affecting the volume fraction and the system viscosity. Here the volume fraction is derived from the flow curves at low concentrations by fitting the zero-shear viscosity with the Einstein–Batchelor equation which provides a parameter k to shift weight concentration to volume fraction. We find that particles with higher PAAc content and crosslinker are characterized by a greater value of k and therefore by larger volume fractions when compared to softer particles. The packing fractions obtained from rheological measurements are compared with those from static light scattering for two PAAc contents revealing a good agreement. Moreover, the behaviour of the viscosity as a function of packing fraction, at room temperature, has highlighted an Arrhenius dependence for microgels synthesized with low PAAc content and a Vogel–Fulcher–Tammann dependence for the highest investigated PAAc concentration. A comparison with the hard spheres behaviour indicates a steepest increase of the viscosity with decreasing particles softness. Finally, the volume fraction dependence of the viscosity at a fixed PAAc and at two different temperatures, below and above the volume phase transition, shows a quantitative agreement with the structural relaxation time measured through dynamic light scattering indicating that interpenetrated polymer network microgels softness can be tuned with PAAc and temperature and that, depending on particle softness, two different routes are followed.