Effect of chemical structure on the subglass relaxation dynamics of biobased polyesters as revealed by dielectric spectroscopy: 2,5-furandicarboxylic acid vs. trans-1,4-cyclohexanedicarboxylic acid.

The chemical structure-dynamics relationship for poly(trimethylene 2,5-furanoate) and poly(trimethylene 1,4-cyclohexanedicarboxylate) was investigated via dielectric spectroscopy and compared with that of poly(trimethylene terephthalate) in order to evaluate the impact on the subglass dynamics of the chemical nature of the ring. Further comparison was accomplished with the neopentyl glycol containing counterparts: poly(neopentyl 2,5-furanoate) and poly(neopentyl 1,4-cyclohexanedicarboxylate). Our study reveals a multimodal nature of the subglass ß process. For the more flexible polymers (containing cyclohexane rings) three modes for the ß process were detected. The faster mode was assigned to the relaxation of the oxygen linked to the aliphatic carbon, the slower one to the link between the aliphatic ring and the ester group, and the third mode to the aliphatic ring. For stiffer polymers (containing aromatic rings), the local modes appear more coupled. This effect is more evident in the polymers with the furan ring where essentially a single ß mode can be resolved.

Combining FES and Exoskeletons in a Hybrid Haptic System for Enhancing VR Experience.

Robotic technology and functional electrical stimulation (FES) have emerged as highly effective rehabilitative techniques for individuals with neuromuscular diseases, showcasting their ability to restore motor functions. Within the proposed study, we developed and tested a new hybrid controller combining an upper-limb exoskeleton with FES to enhance haptic feedback when performing task-oriented and bimanual movement, like pick-and-place, in a virtual environment. We investigated the performance of the proposed approach on eight unimpaired participants providing haptic feedback either only by the exoskeleton or by the hybrid system. The hybrid control presents two different modalities, assistive and resistive, to modulate the perception of the load. FES intensity is calibrated to the subjects' biomechanical properties and it is adjusted in real-time according to the real-time motion of the upper limbs. Experimental results highlighted the ability of the hybrid control to improve kinematic performance: in both hybrid modalities subjects reduced the target matching error(values between 0.048±0.007 m and 0.06±0.006 m) without affecting the normal motion smoothness (SPARC values in the hybrid conditions range from -2.58±0.12 to -3.30±0.13). Moreover, the resistive approach resulted in greater metabolic consumption (1.04±0.03 W/kg), indicating a more realistic experience of lifting a virtual object through FES that increased the perceived weight. The innovation in our hybrid control relies on the modulation of muscular activation during manipulation tasks, which could be a promising approach in the clinical treatment of neuromuscular diseases.

Structure and morphology of thin films of linear aliphatic polyesters prepared by spin-coating.

Thin films, with thicknesses from 10 to 400 nm of linear aliphatic polyesters (X, Y), based on propylenediol (X = 3) and on dicarboxylic acid of different chain length (Y = 2, 3, and 4 CH(2) units) were prepared by spin coating of CHCl(3) polymer solutions with different polymer concentrations. Morphology and structure of the spin coated thin films were investigated by atomic force microscopy (AFM) and by grazing incidence X-ray scattering techniques at small, (GISAXS) and wide angles (GIWAXS). AFM revealed a strong dewetting for all three polymers for coatings thinner than 100 nm. The polymer films are clearly semicrystalline for thicknesses higher than 50 nm. GIWAXS of the thicker films revealed their oriented crystalline nature. An edge-on-lamellae morphology is clearly shown by the AFM-phase images even for relatively thin films. SAXS with the beam parallel to the sample plane also support the presence of lamellae perpendicular to the substrate. The use of a mu-beam helped to interpret the GIWAXS patterns and allowed to obtain oriented WAXS patterns from melt solidified filaments. Thus, a crystal chain packing is proposed for the three polymers and consequently the indexing of the observed reflections. Accordingly, the polymer chains lie parallel to the substrate being the bc plane of the monoclinic crystal unit cell parallel to the substrate.

Flat-on lamellae in spin-coated, stable films of poly(propylene azelate).

Thin films (5-500 nm thick) of the linear aliphatic polyester (3,7) poly(propylene azelate) (PPAz) were prepared by spin-coating of CHCl(3) polymer solutions with different polymer concentrations. The morphology and structure of the spin-coated thin films were investigated by atomic force microscopy (AFM) and by grazing incidence wide-angle X-ray scattering (GIWAXS) techniques. AFM revealed the continuous nature of the flat, spherulitic films which are stable against dewetting even for polymer coatings as thin as 15 nm. GIWAXS patterns revealed a high crystal orientation of the films. A sharp reflection on the meridian whose spacing is related to the polymer chain unit length (c-axis) supports the presence of flat-on lamellae morphology in the whole range of film thicknesses investigated. The flat-on lamellae morphology is also supported by AFM images. A triclinic unit cell with the c*-axis perpendicular to the substrate is proposed for PPAz. The repulsion of the long aliphatic spacer by the Si-substrate is invoked as the main reason for the flat-on morphology observed.

Evidence of early stage precursors of polymer crystals by dielectric spectroscopy.

Dielectric spectra of the polyester poly(propylene succinate) were measured upon crystallization. For this model aliphatic polyester the alpha and beta relaxations appear simultaneously and are well resolved in the experimental frequency window. During isothermal crystallization, this fact allows one to use the beta relaxation to characterize the crystalline structural development while the alpha relaxation provides information about the evolution of the amorphous phase dynamics. In this way structure development and dynamics evolution can be characterized by a single experiment during the crystallization process. The unambiguous analysis of the dielectric loss clearly supports the existence of precursors of crystallization in the induction period.