Solid polymer electrolytes based on chitosan and europium triflate

Solid polymer electrolytes (SPEs) were obtained from chitosan plasticized with glycerol and contained europium (III) trifluoromethanesulfonate salt. The transparent samples were characterized by thermal analysis (DSC and TGA), impedance spectroscopy and electron paramagnetic resonance (EPR). The sample with 55.34 wt.% of europium triflate showed the best ionic conductivity of 1.52 × 10−6 and 7.66 × 10−5 S cm−1 at 30°C and 80°C, respectively. The thermal analysis revealed that the degradation started at around 130–145°C and the weight loss ranged from 20 to 40%. The DSC of the samples showed no Tg, but only a large endothermic peak that was centered between 160 and 200 °C. The EPR analysis showed a broadening of the EPR resonance lines with increasing europium contents in the chitosan membranes due to the magnetic dipole–dipole coupling and spin–spin exchange between the Eu2+ ions. Moreover, the electrolytes based on chitosan and europium triflate presented good flexibility, homogeneity, and transparency.

Polymer electrolyte based on DNA and N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium bis(trifluoromethylsulfonyl)imide

Combining ionic liquids (ILs) with polymers offers the prospect of new applications, where they surpass the performance of conventional media, such as organic solvents, giving advantages in terms of improved safety and a higher operating temperature range. In this work we have investigated the morphology, thermal and electrochemical properties of polymer electrolytes prepared through the addition of con- trolled quantities of the cholinium based IL N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium bis(trifluo- romethylsulfonyl)imide ([N1 1 1 2(OH)] [NTf2]) to a deoxyribonucleic acid (DNA) host network. These novel IL-based electrolytes have been analyzed aiming at applications in electrochemical devices. An optimized sample showed good thermal stability up to 155 °C and a wide electrochemical window of ~3.5 V. The highest conductivity was registered for the DNA[N1 1 1 2(OH)][NTf2] (1:1) (2.82 × 10-5 and 1.09 × 10-3 S cm-1 at 30 and 100 °C, respectively).

Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C2mim][CnSO3], [C2mim][CnSO4] and [C2mim][diCnPO4]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes (SPE) membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10−4 S cm−1 and a wide electrochemical window of ∼ 4.0 V.

Polymer electrolytes for electrochromic devices

Polymer electrolytes are currently the focus of much attention as potential electrolytes in electrochemical devices such as batteries, display devices and sensors. Generically, solid polymer electrolytes (SPEs) are mixtures of salts with soft polar polymers. SPEs have many advantages including high energy density, no risk of leakage, no issues related to the presence of solvent, wide electrochemical stability windows, simplified processability and light weight. With the goal of developing a new family of environmentally friendly multifunctional biohybrid materials displaying high ionic conductivity we have produced in the present work, flexible films based on different polymers or hybrids incorporating different salts. The polymer electrolytes studied here have been characterized by means of Differential Scanning Calorimetry, Thermogravimetric Analysis, X-ray diffraction, Polarized Optical Microscopy, complex impedance spectroscopy and cyclic voltammetry. An evaluation of the performance of the sample with the highest conductivity as electrolyte in all solid-state ECDs was performed.

Desenvolvimento de uma matriz de sensores piezoresistivos baseados em técnicas de impressão

Dissertação de mestrado em Técnicas de Caracterização e Análise Química

Rheological characterization of EVA and HDPE polymer modified bitumens under large deformation at 20 º C

Large amplitude oscillatory shear (LAOS) coupled with Fourier transform rheology (FTR) was used for the first time to characterize the large deformation behavior of selected bituminous binders at 20 C. Two polymer modified bitumens (PMB) containing recycled EVA and HDPE and two unmodified bitumens were tested with LAOS-FTR. The LAOS-FTR response of all binders was compared at same frequency, at same Deborah number (by tuning the frequency to the relaxation time of each binder) and at same phase shift angle d (by tuning the frequency to the one corresponding to d = 50 in the SAOS response of each sample). In all the approaches, LAOS-FTR results allowed to differentiate between all the nonlinear mechanical characteristics of the tested binders. All binders show LAOS-FTR patterns reminiscent from colloidal dispersions and emulsions. EVA PMB was less prone to strain-induced microstructural changes when compared to HDPE PMB which showed larger values of nonlinear FTR parameters for the range of shear strains tested in LAOS.

Estudo da ligação entre componentes estruturais de GFRP (glass fiber reinforced polymer) e componentes estruturais em betão

Dissertação de mestrado integrado em Engenharia Civil

High performance screen printable lithium-ion battery cathode ink based on C-LiFePO4

Lithium-ion battery cathodes have been fabricated by screen-printing through the development of CLiFePO4 inks. It is shown that shear thinning polymer solutions in N-methyl-2-pyrrolidone (NMP) with Newtonian viscosity above 0.4 Pa s are the best binders for formulating a cathode paste with satisfactory film forming properties. The paste shows an elasticity of the order of 500 Pa and, after shear yielding, shows an apparent viscosity of the order of 3 Pa s for shear rates corresponding to those used during screen-printing. The screen-printed cathode produced with a thickness of 26 mm shows a homogeneous distribution of the active material, conductive additive and polymer binder. The total resistance and diffusion coefficient of the cathode are 450 V and 2.5 10 16cm2 s 1, respectively. The developed cathodes show an initial discharge capacity of 48.2 mAh g 1 at 5C and a discharge value of 39.8 mAh g 1 after 50 cycles. The capacity retention of 83% represents 23% of the theoretical value (charge and/or discharge process in twenty minutes), demonstrating the good performance of the battery. Thus, the developed C-LiFePO4 based inks allow to fabricate screen-printed cathodes suitable for printed lithium-ion batteries

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.

Nonlinear frequency response analysis for the diagnosis of polymer electrolyte membrane fuel cells

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2012

Electrochemical oxidation of H 2, CO gas mixtures in polymer-electrolyte-membrane fuel cells

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2014

Hydrogen chloride electrolysis in a polymer-electrolyte-membrane reactor with oxygen-depolarized cathode

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2015

Neurolysis using a carbohydrate polymer gel for the treatment of postoperative neuropathic pain.

Perineural and intraneural fibrosis is thought to be the main cause of failure of the many surgical treatments of neuropathic pain. We have used Adcon-T/N carbohydrate polymer gel for prevention of perineural fibrosis in several parts of the body. In this retrospective study, 54 patients who presented with postoperative neuropathic pain had microsurgical epineural neurolysis and relocation of a terminal neuroma. In 19 of them, the carbohydrate gel was applied at the same time. The mean follow-up was four years and the nerve distribution varied. Postoperative improvement in pain scores (visual analogue scale (VAS) and neuropathic pain scale inventory (NPSI)), sensitivity, overall improvement and satisfaction were equivalent in the two groups, with pain relief in about 80% of the patients. There was no significant beneficial effect in the carbohydrate gel group. Patients treated with this device had a higher infection rate (21 compared with 0, p = 0.01) and delayed wound healing (31.6 compared with 11.8, p = 0.2). We conclude that good long-term pain relief is obtained postoperatively independently of the addition of carbohydrate gel. There was a slight but not significant trend towards profound pain relief with the gel.

Capsule permeability via polymer and protein ingress/egress.

Static incubation tests, where microcapsules and beads are contacted with polymer and protein solutions, have been developed for the characterization of permselective materials applied for bioartificial organs and drug delivery. A combination of polymer ingress, detected by size-exclusion chromatography, and protein ingress/ egress, assessed by gel electrophoresis, provides information regarding the diffusion kinetics, molar mass cutoff(MMCO) and permeability. This represents an improvement over existing permeability measurements that are based on the diffusion of a single type of solute. Specifically, the permeability of capsules based on alginate, cellulose sulfate, polymethylene-co-guanidine were characterized as a function of membrane thickness. Solid alginate beads were also evaluated. The MMCO of these capsules was estimated to be between 80 and 90 kDa using polymers, and between 116-150 kDa with proteins. Apparently, the globular shape of the proteins (radius of gyration (Rg) of 4.2-4.6 nm) facilitates their passage through the membrane, comparatively to the polysaccharide coil conformation (Rg of 6.5-8.3 nm). An increase of the capsule membrane thickness reduced these values. The MMCO of the beads, which do not have a membrane limiting their permselective properties, was higher, between 110 and 200 kDa with dextrans, and between 150 and 220 kDa with proteins. Therefore, although the permeability estimated with biologically relevant molecules is generally higher due to their lower radius of gyration, both the MMCO of synthetic and natural watersoluble polymers correlate well, and can be used as in vitro metrics for the immune protection ability of microcapsules and microbeads. This article shows, to the authors' knowledge, the first reported concordance between permeability measures based on model natural and biological macromolecules.