Aqueous Laponite Clay Dispersions in the Presence of Poly(ethylene oxide) or Poly(propylene oxide) Oligomers and their Triblock Copolymers R. De Lisi M. Gradzielski G. Lazzara S. Milioto N. Muratore S. PreĢvost 10.1021/jp8024073.s001 https://acs.figshare.com/articles/journal_contribution/Aqueous_Laponite_Clay_Dispersions_in_the_Presence_of_Poly_ethylene_oxide_or_Poly_propylene_oxide_Oligomers_and_their_Triblock_Copolymers/2922415 The effect of polyethylene oxide (PEO) or polypropylene oxide (PPO) oligomers of various molecular weight (<i>M</i><sub>w</sub>) as well as of triblock copolymers, based on PEO and PPO blocks, on aqueous laponite RD suspensions was studied with small-angle neutron scattering (SANS). The radius of gyration (<i>R</i><sub>G</sub>) increases for low <i>M</i><sub>w</sub> whereas the opposite occurs for larger <i>M</i><sub>w</sub>. This behavior is explained on the basis that an effective <i>R</i><sub>G</sub> is given by two contributions: (1) the size of the particles coated with the polymer and (2) the interactions between the laponite RD particles which are attractive for small and repulsive for large polymers. The SANS curves in the whole <i>Q</i>-range are well described by a model of noninteracting polydisperse core + shell disks, where the thickness of the polymer layer increases with the <i>M</i><sub>w</sub>. The adsorbed polymer is in a more compact conformation compared to a random coil distribution while the fraction of the polymer in the shell formed around the laponite RD particles is nearly independent of <i>M</i><sub>w</sub>. For increasing laponite RD amounts, at a given polymer composition, the thickness of the polymer slightly changes. In some cases, where also gelation is sped up, a structure factor with attractive interaction was employed which allowed to evaluate the attractive forces between the laponite RD particles. The gelation time was determined for mixtures at fixed copolymer and laponite RD concentrations. Surprisingly, it is observed that gels are formed despite the fact that the binding sites of the laponite RD particles are almost covered but the polymer size is too small to prevent aggregation. The gelation rate is correlated to structure and thermodynamics of these systems. Namely, when the balance between the steric forces and the depletion attractive forces undergoes an abrupt change the gelation time also undergoes a sharp variation. For lower and comparable <i>M</i><sub>w</sub>, PPO speeds up the gelation more efficiently than PEO while for higher <i>M</i><sub>w</sub> the gelation kinetics is slowed down again. Interestingly, copolymers of PEO and PPO blocks do not induce gelation in the time-window where the homopolymers do. 2008-08-07 00:00:00 Aqueous Laponite Clay Dispersions RG polymer layer increases Mw PEO PPO blocks laponite RD suspensions noninteracting polydisperse core laponite RD amounts oxide laponite RD concentrations SANS gelation time Triblock CopolymersThe effect laponite RD particles