Mechanical behaviour analysis of polyester polymer mortars modified with recycled GFRP waste materials

In this study the effect of incorporation of recycled glass-fibre reinforced polymer (GFRP) waste materials, obtained by means of milling processes, on mechanical behaviour of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste powder and fibres, with distinct size gradings, were incorporated into polyester based mortars as sand aggregates and filler replacements. Flexural and compressive loading capacities were evaluated and found better than unmodified polymer mortars. GFRP modified polyester based mortars also show a less brittle behaviour, with retention of some loading capacity after peak load. Obtained results highlight the high potential of recycled GFRP waste materials as efficient and sustainable reinforcement and admixture for polymer concrete and mortars composites, constituting an emergent waste management solution.

GFRP waste reinforced polymer mortars: a new waste management solution for GFRP scrap material

To date, glass fibre reinforced polymer (GFRP) waste recycling is very limited and restricted by thermoset nature of binder matrix and lack of economically viable enduse applications for the recyclates. In this study, efforts were made in order to recycle grinded GFRP waste proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, a mix of powdered and fibrous materials, were incorporated into polyester based mortars as fine aggregate and filler replacements, at different load contents (between 4% up to 12% of total mass) and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Test results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse in concrete-polymer composites.

Rheo-NMR study of water-based cellulose liquid crystal system at high shear rates

Since long ago cellulosic lyotropic liquid crystals were thought as potential materials to produce fibers competitive with spidersilk or Kevlar, yet the processing of high modulus materials from cellulose-based precursors was hampered by their complex rheological behavior. In this work, by using the Rheo-NMR technique, which combines deuterium NMR with rheology, we investigate the high shear rate regimes that may be of interest to the industrial processing of these materials. Whereas the low shear rate regimes were already investigated by this technique in different works [1-4], the high shear rates range is still lacking a detailed study. This work focuses on the orientational order in the system both under shear and subsequent relaxation process arising after shear cessation through the analysis of deuterium spectra from the deuterated solvent water. At the analyzed shear rates the cholesteric order is suppressed and a flow-aligned nematic is observed which for the higher shear rates develops after certain time periodic perturbations that transiently annihilate the order in the system. During relaxation the flow aligned nematic starts losing order due to the onset of the cholesteric helices leading to a period of very low order where cholesteric helices with different orientations are forming from the aligned nematic, followed in the final stage by an increase in order at long relaxation times corresponding to the development of aligned cholesteric domains. This study sheds light on the complex rheological behavior of chiral nematic cellulose-based systems and opens ways to improve its processing. (C) 2015 Elsevier Ltd. All rights reserved.

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

Development of thermoresponsive (polysulfone/polyacrylonitrile) - based membranes for bioseparation processes

Mestrado integrado em Engenharia Química e Bioquímica

Development of 2-oxazoline-based hydrogels and porous polyester microparticles in scCO2

Thesis submitted to Faculdade de Ciências e Tecnologia from Universidade Nova de Lisboa in partial fulfillment of the requirements for the obtention of the degree of Master of Science in Biotechnology

Development of a piezoelectric biosensor based on PVDF films

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Graphene-based biomimetic materials targeting urine metabolite as potential cancer biomarker: Application over different conductive materials for potentiometric transduction

This work presents a novel surface Smart Polymer Antibody Material (SPAM) for Carnitine (CRT, a potential biomarker of ovarian cancer), tested for the first time as ionophore in potentiometric electrodes of unconventional configuration. The SPAM material consisted of a 3D polymeric network created by surface imprinting on graphene layers. The polymer was obtained by radical polymerization of (vinylbenzyl) trimethylammonium chloride and 4-styrenesulfonic acid (signaling the binding sites), and vinyl pivalate and ethylene glycol dimethacrylate (surroundings). Non-imprinted material (NIM) was prepared as control, by excluding the template from the procedure. These materials were then used to produce several plasticized PVC membranes, testing the relevance of including the SPAM as ionophore, and the need for a charged lipophilic additive. The membranes were casted over solid conductive supports of graphite or ITO/FTO. The effect of pH upon the potentiometric response was evaluated for different pHs (2-9) with different buffer compositions. Overall, the best performance was achieved for membranes with SPAM ionophore, having a cationic lipophilic additive and tested in HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) buffer, pH 5.1. Better slopes were achieved when the membrane was casted on conductive glass (-57.4 mV/decade), while the best detection limits were obtained for graphite-based conductive supports (3.6 × 10−5mol/L). Good selectivity was observed against BSA, ascorbic acid, glucose, creatinine and urea, tested for concentrations up to their normal physiologic levels in urine. The application of the devices to the analysis of spiked samples showed recoveries ranging from 91% (± 6.8%) to 118% (± 11.2%). Overall, the combination of the SPAM sensory material with a suitable selective membrane composition and electrode design has lead to a promising tool for point-of-care applications.

Electrochemical biosensor based on biomimetic material for myoglobin detection

A novel reusable molecularly imprinted polymer (MIP) assembled on a polymeric layer of carboxylated poly(vinyl chloride) (PVCsingle bondCOOH) for myoglobin (Myo) detection was developed. This polymer was casted on the gold working area of a screen printed electrode (Au-SPE), creating a novel disposable device relying on plastic antibodies. Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and Fourier transform infrared spectroscopy (FTIR) studies confirmed the surface modification. The MIP/Au-SPE devices displayed a linear behaviour in EIS from 0.852 to 4.26 μg mL−1, of positive slope 6.50 ± 1.48 (kΩ mL μg−1). The limit of detection was 2.25 μg mL−1. Square wave voltammetric (SWV) assays were made in parallel and showed linear responses between 1.1 and 2.98 μg mL−1. A current decrease was observed against Myo concentration, producing average slopes of −0.28 ± 0.038 μA mL μg−1. MIP/Au-SPE also showed good results in terms of selectivity. The error% found for each interfering species were 7% for troponin T (TnT), 11% for bovine serum albumin (BSA) and 2% for creatine kinase MB (CKMB), respectively. Overall, the technical modification over the Au-SPE was found a suitable approach for screening Myo in biological fluids.

Label-free Detection of Microcystin-LR in Waters Using Real-Time Potentiometric Biosensors Based on Single-Walled Carbon Nanotubes Imprinted Polymers

Microcystin-LR (MC-LR) is a dangerous toxin found in environmental waters, quantified by high performance liquid chromatography and/or enzyme-linked immunosorbent assays. Quick, low cost and on-site analysis is thus required to ensure human safety and wide screening programs. This work proposes label-free potentiometric sensors made of solid-contact electrodes coated with a surface imprinted polymer on the surface of Multi-Walled Carbon NanoTubes (CNTs) incorporated in a polyvinyl chloride membrane. The imprinting effect was checked by using non-imprinted materials. The MC-LR sensitive sensors were evaluated, characterized and applied successfully in spiked environmental waters. The presented method offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Carnitine tailored Sensors on Surface Molecular Imprinting based on Graphene layers

III Jornadas de Electroquímica e Inovação (Electroquímica e Nanomateriais), na Universidade de Trás-os-Montes e Alto Douro, Vila Real, 16 a 17 de Setembro de 2013

Host-Tailored Sensors for Carnitine Potentiometric Measurements based on Surface Molecular Imprinting

Graduate Student Symposium on Molecular Imprinting 2013, na Queen’s University, Belfast, United Kingdom, 15 a 17 de Agosto de 2013

Re-Use Assessment of Thermoset Composite Wastes as Aggregate and Filler Replacement for Concrete-Polymer Composite Materials: A case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.

Development of chitosan-based microparticles for pulmonary drug delivery

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica