Reusability assessment of thermoset polymeric composite wastes as reinforcement and filler replacement for polymer concrete materials

The development and applications of thermoset polymeric composites, namely fiber reinforced polymers (FRP), have shifted in the last decades more and more into the mass market [1]. Production and consume have increased tremendously mainly for the construction, transportation and automobile sectors [2, 3]. Although the many successful uses of thermoset composite materials, recycling process of byproducts and end of lifecycle products constitutes a more difficult issue. The perceived lack of recyclability of composite materials is now increasingly important and seen as a key barrier to the development or even continued used of these materials in some markets.

New recycling approaches for thermoset polymeric composite wastes – an experimental study on polyester based concrete materials filled with fibre reinforced plastic recyclates

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

PLSR Models for Mechanical Strengths of Concrete Composite Materials Reinforced with Pultrusion Wastes

In this paper, we present two Partial Least Squares Regression (PLSR) models for compressive and flexural strength responses of a concrete composite material reinforced with pultrusion wastes. The main objective is to characterize this cost-effective waste management solution for glass fiber reinforced polymer (GFRP) pultrusion wastes and end-of-life products that will lead, thereby, to a more sustainable composite materials industry. The experiments took into account formulations with the incorporation of three different weight contents of GFRP waste materials into polyester based mortars, as sand aggregate and filler replacements, two waste particle size grades and the incorporation of silane adhesion promoter into the polyester resin matrix in order to improve binder aggregates interfaces. The regression models were achieved for these data and two latent variables were identified as suitable, with a 95% confidence level. This technological option, for improving the quality of GFRP filled polymer mortars, is viable thus opening a door to selective recycling of GFRP waste and its use in the production of concrete-polymer based products. However, further and complementary studies will be necessary to confirm the technical and economic viability of the process.

Waste recovery into activated carbon for water purification from heavy metals

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química Pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecn

An experimental study on recycling and reuse of pultruded composite material wastes

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remoulded, and complex composition of the composite itself. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. 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, 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, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behavior over unmodified polyester based mortars, thus indicating the feasibility of the GFRP industrial waste reuse into concrete-polymer composite materials.

Post-processing Techniques in Free Boundary Flows during Liquid Composite Moulding Processes

Post-processing a finite element solution is a well-known technique, which consists in a recalculation of the originally obtained quantities such that the rate of convergence increases without the need for expensive remeshing techniques. Postprocessing is especially effective in problems where better accuracy is required for derivatives of nodal variables in regions where Dirichlet essential boundary condition is imposed strongly. Consequently such an approach can be exceptionally good in modelling of resin infiltration under quasi steady-state assumption by remeshing techniques and with explicit time integration, because only the free-front normal velocities are necessary to advance the resin front to the next position. The new contribution is the post-processing analysis and implementation of the freeboundary velocities of mesolevel infiltration analysis. Such implementation ensures better accuracy on even coarser meshes, which in consequence reduces the computational time also by the possibility of employing larger time steps.

Numerical Method to Predict Void Formation during The Liquid Composite Molding Process

Void formation during the injection phase of the liquid composite molding process can be explained as a consequence of the non-uniformity of the flow front progression. This is due to the dual porosity within the fiber perform (spacing between the fiber tows is much larger than between the fibers within in a tow) and therefore the best explanation can be provided by a mesolevel analysis, where the characteristic dimension is given by the fiber tow diameter of the order of millimeters. In mesolevel analysis, liquid impregnation along two different scales; inside fiber tows and within the open spaces between the fiber tows must be considered and the coupling between the flow regimes must be addressed. In such cases, it is extremely important to account correctly for the surface tension effects, which can be modeled as capillary pressure applied at the flow front. Numerical implementation of such boundary conditions leads to illposing of the problem, in terms of the weak classical as well as stabilized formulation. As a consequence, there is an error in mass conservation accumulated especially along the free flow front. A numerical procedure was formulated and is implemented in an existing Free Boundary Program to reduce this error significantly.

Catalytic oxidation of cyclohexane with hydrogen peroxide and a tetracopper(II) complex in an ionic liquid

The catalytic peroxidative oxidation (with H2O2) of cyclohexane in an ionic liquid (IL) using the tetracopper(II) complex [(CuL)2(μ4-O,O′,O′′,O′′′-CDC)]2·2H2O [HL = 2-(2-pyridylmethyleneamino)benzenesulfonic acid, CDC = cyclohexane-1,4-dicarboxylate] as a catalyst is reported. Significant improvements on the catalytic performance, in terms of product yield (up to 36%), TON (up to 529), reaction time, selectivity towards cyclohexanone and easy recycling (negligible loss in activity after three consecutive runs), are observed using 1-butyl-3-methylimidazolium hexafluorophosphate as the chosen IL instead of a molecular organic solvent including the commonly used acetonitrile. The catalytic behaviors in the IL and in different molecular solvents are discussed.

Enantiomeric fraction evaluation of pharmaceuticals in environmentalmatrices by liquid chromatography-tandem mass spectrometry

The interest for environmental fate assessment of chiral pharmaceuticals is increasing and enantioselective analytical methods are mandatory. This study presents an enantioselective analytical method for the quantification of seven pairs of enantiomers of pharmaceuticals and a pair of a metabolite. The selected chiral pharmaceuticals belong to three different therapeutic classes, namely selective serotonin reuptake inhibitors (venlafaxine, fluoxetine and its metabolite norfluoxetine), beta-blockers (alprenolol, bisoprolol, metoprolol, propranolol) and a beta2-adrenergic agonist (salbutamol). The analytical method was based on solid phase extraction followed by liquid chromatography tandem mass spectrometry with a triple quadrupole analyser. Briefly, Oasis® MCX cartridges were used to preconcentrate 250 mL of water samples and the reconstituted extracts were analysed with a Chirobiotic™ V under reversed mode. The effluent of a laboratory-scale aerobic granular sludge sequencing batch reactor (AGS-SBR) was used to validate the method. Linearity (r2 > 0.99), selectivity and sensitivity were achieved in the range of 20–400 ng L−1 for all enantiomers, except for norfluoxetine enantiomers which range covered 30–400 ng L−1. The method detection limits were between 0.65 and 11.5 ng L−1 and the method quantification limits were between 1.98 and 19.7 ng L−1. The identity of all enantiomers was confirmed using two MS/MS transitions and its ion ratios, according to European Commission Decision 2002/657/EC. This method was successfully applied to evaluate effluents of wastewater treatment plants (WWTP) in Portugal. Venlafaxine and fluoxetine were quantified as non-racemic mixtures (enantiomeric fraction ≠ 0.5). The enantioselective validated method was able to monitor chiral pharmaceuticals in WWTP effluents and has potential to assess the enantioselective biodegradation in bioreactors. Further application in environmental matrices as surface and estuarine waters can be exploited.

Utilization of food industry wastes for the production of zero-valent iron nanoparticles

The proper disposal of the several types of wastes produced in industrial activities increases production costs. As a consequence, it is common to develop strategies to reuse these wastes in the same process and in different processes or to transform them for use in other processes. This work combines the needs for new synthesis methods of nanomaterials and the reduction of production cost using wastes from citrine juice (orange, lime, lemon and mandarin) to produce a new added value product, green zero-valent iron nanoparticles that can be used in several applications, including environmental remediation. The results indicate that extracts of the tested fruit wastes (peel, albedo and pulp fractions) can be used to produce zero-valent iron nanoparticles (nZVIs). This shows that these wastes can be an added value product. The resulting nZVIs had sizes ranging from 3 up to 300 nm and distinct reactivities (pulp > peel > albedo extracts). All the studied nanoparticles did not present a significant agglomeration/settling tendency when compared to similar nanoparticles, which indicates that they remain in suspension and retain their reactivity.

A cellulosic liquid crystal pool for cellulose nanocrystals: structure and molecular dynamics at high shear rates

Cellulose and its derivatives, such as hydroxypropylcellulose (HPC) have been studied for a long time but they are still not well understood particularly in liquid crystalline solutions. These systems can be at the origin of networks with properties similar to liquid crystalline (LC) elastomers. The films produced from LC solutions can be manipulated by the action of moisture allowing for instance the development of a soft motor (Geng et al., 2013) driven by humidity. Cellulose nanocrystals (CNC), which combine cellulose properties with the specific characteristics of nanoscale materials, have been mainly studied for their potential as a reinforcing agent. Suspensions of CNC can also self-order originating a liquid-crystalline chiral nematic phases. Considering the liquid crystalline features that both LC-HPC and CNC can acquire, we prepared LC-HPC/CNC solutions with different CNC contents (1,2 and 5 wt.%). The effect of the CNC into the LC-HPC matrix was determined by coupling rheology and NMR spectroscopy - Rheo-NMR a technique tailored to analyse orientational order in sheared systems. (C) 2015 Elsevier Ltd. All rights reserved.

A case study undertaken recycling & reuse of glass fiber reinforced thermoset polumer wastes of composite materials industry

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: crosslinked nature of thermoset resins, which cannot be remoulded, and complex composition of the composite itself. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. 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, 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, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of the GFRP industrial waste reuse into concrete-polymer composite materials.

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.

Rheo-optical characterization of liquid crystalline acetoxypropylcellulose melt undergoing large shear flow and relaxation after flow cessation

The rheological and structural characteristics of acetoxypropylcellulose (APC) nematic melt are studied at shear rates ranging from 10 s(-1) to 1000 s(-1) which are relevant to extrusion based processes. APC shows a monotonic shear thinning behavior over the range of shear rates tested. The negative extrudate-swell shows a minimum when a critical shear rate (gamma) over dot(c) is reached. For shear rates smaller than (gamma) over dot(c), the flow-induced texture consists of two set of bands aligned parallel and normal to the flow direction. At shear rates larger than (gamma) over dot(c), the flow induced texture is reminiscent of a 2 fluids structure. Close to the shearing walls, domains elongated along the flow direction and stacked along the vorticity are imaged with POM, whereas SALS patterns indicate that the bulk of the sheared APC is made of elliptical domains oriented along the vorticity. No full nematic alignment is achieved at the largest shear rate tested. Below (gamma) over dot(c), the stress relaxation is described by a stretched exponential. Above (gamma) over dot(c), the stress relaxation is described by a fast and a slow process. The latter coincides with the growth of normal bands thicknesses, as the APC texture after flow cessation consists of two types of bands with parallel and normal orientations relative to the flow direction. Both bands thicknesses do not depend on the applied shear rate, in contrast to their orientation. (C) 2015 Elsevier Ltd. All rights reserved.

Electrorheological characterization of dispersions in silicone oil of encapsulated liquid crystal 4-n-penthyl-4 '-cyanobiphenyl in polyvinyl alcohol and in silica

The electrorheological (ER) effect is known as the change in the apparent viscosity upon the application of an external electric field perpendicular to the flow direction. In this work we present the electrorheological behaviour of suspensions in silicone oil of two different dispersed phases: foams of liquid crystal 4-n-penthyl-4'-cyanobiphenyl (5CB) encapsulated in polyvinyl alcohol (PVA) and nano/microspheres of 5CB encapsulated in silica. We will present the viscosity curves under the application of an electric field ranging between 0 and 3 kV mm(-1). The ER effect was observed for the suspensions of 5CB/PVA but not in the case of 5CB/silica. For the case of the suspensions of 5CB/PVA, the effect of the viscosity of the continuum phase and the concentration of the dispersed phase was analysed, showing that the enhancement of the viscosity of the suspension increases with the concentration, as expected, however the continuum phase viscosity has no significant effect, at least in the investigated viscosity range.