Here we report the preparation and characterization of nanostructured thermo-responsive poly(acrylamide) (PAM)-based hydrogels. The addition of slightly crosslinked poly(N-isopropylacrylamide) (PNIPA) nanogels to AM reactive aqueous solution produces nanostructured hydrogels that exhibit a volume phase transition temperature (T_VPT). Their swelling kinetics, T_VPT's and mechanical properties at the equilibrium-swollen state (H_eq) are investigated as a function of the concentration of PNIPA nanogels in the nanostructured hydrogels. Nanostructured hydrogels with PNIPA nanogels/AM mass ratios of 20/80 and above exhibit higher H_eq and longer time to reach the equilibrium swelling than those of the conventional PAM hydrogels. However, the PNIPA nanogels possess thermo-responsive character missing in conventional PAM hydrogels. The T_VPT of nanostructured hydrogels depends on PNIPA nanogel content but their elastic and Young moduli are larger than those of conventional hydrogels at similar swelling ratios. Swelling kinetics, T_VPT, and mechanical properties are explained in terms of the controlled in-homogeneities introduced by the PNIPA nanogels during the polymerization.

To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution (WCD) of copolymer chains. Here, the styrene-n-butyl acrylate (S/BA) system was polymerized by means of a semicontinuous emulsion process, varying the composition of the comonomer feed to obtain forced composition copolymers (FCCs). Five different feeding profiles were used, searching for a scheme to obtain chains rich in S (looking for considerable modulus), and chains rich in BA (looking for large deformation) as a technique to achieve synergy in copolymer properties; the mechanostatic and dynamic characterization discloses the correspondence between WCD and the bulk properties. ¹H-nuclear magnetic resonance (¹H-NMR) analysis enabled the determination of the cumulative copolymer composition characterization, required to estimate the WCD. The static test (stress-strain) and dynamic mechanical analysis (DMA) were performed following normed procedures. This is the first report that shows very diverse mechanostatic performances of copolymers obtained using the same chemical system and global comonomer composition, forming a comprehensive failure envelope, even though the tests were carried out at the same temperature and cross head speed. The principles for synergic performance can be applied to controlled radical copolymerization, designing the composition variation in individual molecules along the conversion.

The shear thickening behavior of dilute micellar solutions of hexadecyltrimethylammonium-type surfactants with different counterions (tosylate, 3- and 4-fluorobenzoate, vinylbenzoate and salicylate) and of n-alkyltetradecylammonium bromide (C_nTAB), with n = 14, 16 and 18, is examined here. These solutions undergo a shear thickening transition due to the formation of shear-induced structures (SISs) in the shear range studied. Here we report a relationship between the shear thickening intensity and the differences in the hydrophobicity of counterions according to the Hofmeister-like anion series, which leads to a master flow diagram. This master flow diagram is produced by plotting a normalized shear thickening intensity (I_η − 1)/(I_max − 1) versus C_D/C_D,max, where I_η is the shear-thickening intensity, defined as the largest viscosity obtained in the shear-thickening transition (STT) at a given surfactant concentration C_D divided by the Newtonian viscosity η₀, and I_max is the largest intensity value obtained in the STT at a surfactant concentration C_D,max. The master flow diagram is built using several cetyltrimethylammonium-type surfactants with different counterions, according to a Hofmeister-like series, and by n-alkyltetradecylammonium bromide surfactants with different alkyl chain lengths.

This paper aims at exploring the complexities of students’ interaction in a collaborative learning task set within a CLIL unit in the EFL classroom. By way of illustration, a sample from a 4th year classroom grade in a secondary school of Catalonia has been collected. The paper examines, through the students’ outcome, the impact of cooperative learning in a content-rich information swap task and discusses the role of content and language integrated learning in the classroom. This paper concludes with several implications for research and practice.