Deamination of Polyols from the Glycolysis of Polyurethane.

Methylenedianiline (MDA) is a secondary, undesired, product of the glycolysis process of polyurethane (PU) scraps due to hydrolysis and pyrolysis side reactions. As an aromatic and carcinogen amine, MDA poses different problems in handling, transporting, and labelling recycled polyols derived from glycolysis, hindering the closure of PU recycling loop. Aiming to provide a solution to this issue, in this work different deaminating agents (DAs) were investigated with the purpose of analyzing their reactivity with MDA. A first part of the study was devoted to the analysis of MDA formation as a function of reaction time and catalyst concentration (potassium acetate) during glycolysis. It was observed that the amount of MDA increases almost linearly with the extent of PU depolymerization and catalyst content. Among the DAs analyzed 2-ethylhexyl glycidyl ether (2-EHGE), and acetic anhydride (Ac2 O) showed interesting performance, which allowed MDA content to be diminished below the limit for labelling prescription in 30 minutes. PU rigid foams were, therefore, synthesized from the corresponding recycled products and characterized in terms of thermal and mechanical performance. Ac2 O-deaminated polyols led to structurally unstable foams with poor compressive strength, while 2-EHGE-deaminated products allowed the production of foams with improved mechanical performance and unaltered thermal conductivity.

Chemical Recycling of Polyurethane Waste via a Microwave-Assisted Glycolysis Process.

In this work, we explored a microwave-assisted glycolysis process to chemically recycle rigid polyurethane (PU) foam waste to obtain a single-phase product with suitable physio-chemical properties as a secondary raw material for the preparation of new rigid PU products. Such an approach was compared to a conventionally heated (ConvH) process, analyzing the performances of different catalysts. The use of microwaves allowed a 94% decrease in the reaction time scale of rigid PU depolymerization, with a concurrent 45% reduction in energy expense. By using a PU/diethylene glycol mass ratio of 1.5, best performances were obtained with a 30 mmol/100gPU potassium acetate concentration, both in terms of the product viscosity and aromatic amine byproduct content. The glycolysis products recovered were employed in substitution to virgin polyol for rigid PU foam preparation, showing improved compressive strength and comparable thermal insulation properties up to a 30% content with respect to the traditional non-recycled counterpart.

Ultrasound-Promoted Abatement of Formaldehyde in Liquid Phase with Electrospun Nanostructured Membranes: The Synergy of Combined AOPs.

The present work investigates the effect of ultrasounds in the performance of combined advanced oxidation processes (AOPs) on the degradation of formaldehyde (HCHO)-polluted aqueous solutions for potential application in wastewater treatment. Different heterogeneous nanostructured catalysts based on TiO2 and FeSO4 for photocatalysis and the Fenton process were employed after electrospray deposition on electrospun nanofibrous membranes. Such systems were tested, without the use of any added hydrogen peroxide, by varying the combinations among the selected AOPs in a batch reactor configuration. The results show that, in the absence of a Fenton reaction, ultrasounds provided a significantly increased formaldehyde photocatalytic abatement, probably by increasing the concentration of active species through a different set of reactions while providing a favorable mass transfer regime by the cavitational effect. Due to the faster kinetics of the photo-Fenton process, thanks to its partial homogeneous nature, such a beneficial effect is more limited for the sono-photo-Fenton configuration. On the other hand, the employment of a sono-photocatalytic-Fenton process revealed a synergic effect that provided the best results, reducing the formaldehyde concentration to less than 99% after 240 min. Further analysis showed that, due to a mutual influence, only a tailored TiO2/FeSO4 ratio on the membranes was able to display the best performance.

Investigation and Optimization of Vacuum Plasma Treatment of PA66 Fabric for Reduced Fire Retardant Consumption.

Flame retardant (FR) textiles were obtained by surface treatments of polyamide 66 fabrics with microwave (MW) plasma technology in order to reduce the amount of FR involved in the fabric finishing process. More specifically, MW vacuum plasma was employed for polymer surface activation by using a helium/oxygen (He/O2) gas mixture, evaluating the effect of different treatment parameters on the affinity toward thiourea impregnation. Surface fabric modification was investigated both in terms of uniformity and increased thiourea absorption by infrared spectroscopy, wicking properties, and gravimetric characterization to define an operative window for plasma treatment conditions. According to the results obtained, the dry add-on content of thiourea improved up to 38%, thanks to the increase of the fabric surface activation. The effectiveness of plasma treatment resulted in an absolute increase up to 2% in limiting oxygen index (LOI) performance with respect to untreated fabric. As a consequence, a drastic reduction of 50% in thiourea concentration was required to achieve a similar fire retardant performance for plasma-treated fabric. On the basis of these preliminary results, a design of experiment (DoE) methodology was applied to the selected parameters to build a suitable response surface, experimentally validated, and to identify optimized treatment conditions. At the end, a final LOI index up to 43% has been reached.

Effects of Solvent and Electrospinning Parameters on the Morphology and Piezoelectric Properties of PVDF Nanofibrous Membrane.

PVDF electrospun membranes were prepared by employing different mixtures of solvents and diverse electrospinning parameters. A comprehensive investigation was carried out, including morphology, nanofiber diameter, crystallinity, ß-phase fraction, and piezoelectric response under external mechanical strain. It was demonstrated that by using low-toxicity DMSO as the solvent, PVDF membranes with good morphology (bead-free, smooth surface, and uniform nanofiber) can be obtained. All the fabricated membranes showed crystallinity and ß-phase fraction above 48% and 80%, respectively; therefore, electrospinning is a good method for preparing PVDF membranes with the piezoelectric properties. Moreover, we considered a potential effect of the solvent properties and the electrospinning parameters on the final piezoelectric properties. When PVDF membranes with different ß-phase fractions and crystallinity values are applied to make the piezoelectric transducers, various piezoelectric voltage outputs can be obtained. This paper provides an effective and efficient strategy for regulating the piezoelectric properties of PVDF electrospun membranes by controlling both solvent dipole moment and process parameters. To the best of our knowledge, this is the first time that the influence of a solvent's dipole moment on the piezoelectric properties of electrospun materials has been reported.

Combined AOPs for Formaldehyde Degradation Using Heterogeneous Nanostructured Catalysts.

In this paper we studied the combination of advanced oxidation processes (AOPs), i.e., TiO2-based photocatalysis and photo-Fenton process, on the degradation of aqueous solutions containing a low (90 ppm) concentration of formaldehyde. Heterogeneous nanostructured catalysts, supported on polymeric nanofibers, were used; for comparison, some homogeneous or partly heterogeneous systems were also analyzed. Furthermore, to make the process more sustainable (in terms of costs and safety) no hydrogen peroxide was added to the system. The results showed that the combination of AOPs gave a synergy since the presence of iron was beneficial in promoting the photocatalytic activity of TiO2 while TiO2 was beneficial in promoting the photo-Fenton reaction. Moreover, very good results were obtained using fully heterogeneous nanostructured catalysts (based on TiO2 and FeSO4), without the need to add H2O2.

Influence of Different Carbon-Based Fillers on Electrical and Mechanical Properties of a PC/ABS Blend.

The present work examines the influence of different carbon-based fillers on the performance of electrically conductive polymer blend composites. More specifically, we examined and compared the effects of graphene (GR), carbon nanotubes (CNTs) and carbon black (CB) on a PC/ABS matrix by morphological investigation, electrical and physic-mechanical characterization. Electrical analyses showed volume resistivity decreased when the CNTs and CB content were increased, although the use of melt-mixed GR did not really influence this property. For the latter, solution blending was found to be more suitable to obtain better GR dispersion, and it obtained electrical percolation with a graphene content ranging from 0.5% to 1% by weight, depending on the solvent removal method that was applied. There was a gradual improvement in all of the composites' dielectric properties, in terms of loss factor, with temperature and the concentration of the filler. As expected, the use of rigid fillers increased the composite stiffness, which is reflected in a continuous increment in the composites' modulus of elasticity. The improvements in tensile strength and modulus were coupled with a reduction in impact strength, indicating a decrease in polymer toughness and flexibility. TEM micrographs allowed us to confirm previous results from studies on filler dispersion. According to this study and the comparison of the three carbon-based fillers, CNTs are the best filler choice in terms of electrical and mechanical performance.

Life Cycle Assessment Framework To Support the Design of Biobased Rigid Polyurethane Foams.

A methodological framework implementing laboratory activities and life cycle assessment is presented and applied to determine which parameters should be considered to develop biobased rigid polyurethane foams for thermal insulation with improved environmental performances when compared to their fossil counterparts. The framework was applied to six partially biobased (produced from bio-based polyols obtained from azelaic acid and/or lignin) and one fossil-based formulations. A comprehensive set of impact assessment categories was investigated including uncertainty and sensitivity analysis. Results proved that physical characteristics such as thermal conductivity and density are the most important variable to be optimized to guarantee better environmental performances of biobased polyurethane rigid foams for thermal insulation. Care should be taken with reference to ozone depletion potential, marine eutrophication, and abiotic depletion potential because of the uncertainty related to their results. The methylene diphenyl diisocyanate and foam production process were identified as the major sources of impacts. Overall environmental superiority of biobased polyurethanes cannot always be claimed with respect to their fossil counterpart.

Investigation of Plasma-Assisted Functionalization of Graphitic Materials for Epoxy Composites.

In this study we evaluated the effect of microwave vacuum plasma for the surface functionalization of graphitic fillers (graphite and graphene); we also showed the effect of the functionalization on the mechanical and electrical properties of epoxy composites. Optimized conditions of plasma treatment were defined to obtain high plasma density and increased surface hydrophilicity of the fillers, with high stability of functionalization over time and temperature. However, the extent of such treatments proved to be limited by the high temperatures involved in the curing process of the resin. The use of specific gas mixtures (He/O2) during functionalization and the use of a high surface filler (graphene) can partially limit these negative effects thanks to the higher thermal stability of the induced functionalization. As a consequence, mechanical tests on graphene filled epoxies showed limited improvements in flexural properties while electrical resistivity is slightly increased with a shift of the percolation threshold towards higher filler concentration.

The Effect of Different Compatibilizers on the Properties of a Post-Industrial PC/PET Blend.

The substitution of virgin resins by recycled ones is a worldwide tendency that is supported by the fluctuation of oil prices and the transition to a circular economy. Polymeric blends have been intensively studied because of their ability to provide tailored properties for particular applications. However, in their design phases, the issue of end-life re-use had not been well addressed, and now difficulties in their recycling are arising. In this study, we investigated the effect of three different compatibilizers: two chain extenders (CEs), (1) a styrene-acrylic oligomer (ESAo), and (2) methylene diphenyl diisocyanate (MDI) and an impact strength modifier, (3) an ethylene copolymer (EMAco), for the recycle of a post-industrial polycarbonate/polyethylene terephthalate (PC/PET) blend. The materials were prepared by reactive extrusion and characterized by intrinsic viscosity (IV) measurements, mechanical tests, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy analysis (FTIR), and transmission electron microscopy (TEM). The introduction of each additive has been demonstrated to improve the compatibility between PET and PC in the post-industrial blend, leading to enhanced mechanical properties. The IV measurements increased to values that were comparable to the virgin material. In addition, CEs affected the crystallization of PET (as they reduced the degree of crystallinity), while EMAco acted as a nucleating agent. Morphological analysis enabled confirming the compatibilization effects induced by the tested additives.

Microwave-assisted synthesis of isosorbide-derived diols for the preparation of thermally stable thermoplastic polyurethane.

In order to prepare thermally stable isosorbide-derived thermoplastic polyurethane, the synthesis of two new chiral exo-exo configured diols, prepared from isosorbide, and two types of diphenols (bisphenol A and thiodiphenol) was described. The synthesis conditions were optimized under conventional heating and microwave irradiations. To prove their suitability in polymerization, these monomers were successfully polymerized using 4,4'-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). Both monomers and polymers have been studied by NMR, FT-IR, TGA, DSC; intrinsic viscosity of polymers has also been determined. The results showed the effectiveness of the synthetic strategy proposed; moreover, a dramatic reduction of the reaction time and an important improvement of the monomers yield using microwave irradiation have been demonstrated. The monomers, as well as the polymers, showed excellent thermal stability both in air and nitrogen. It was also shown that the introduction of sulphur in the polyurethane backbone was effective in delaying the onset of degradation as well as the degradation rate.

Synthesis and Process Optimization of Electrospun PEEK-Sulfonated Nanofibers by Response Surface Methodology.

In this study electrospun nanofibers of partially sulfonated polyether ether ketone have been produced as a preliminary step for a possible development of composite proton exchange membranes for fuel cells. Response surface methodology has been employed for the modelling and optimization of the electrospinning process, using a Box-Behnken design. The investigation, based on a second order polynomial model, has been focused on the analysis of the effect of both process (voltage, tip-to-collector distance, flow rate) and material (sulfonation degree) variables on the mean fiber diameter. The final model has been verified by a series of statistical tests on the residuals and validated by a comparison procedure of samples at different sulfonation degrees, realized according to optimized conditions, for the production of homogeneous thin nanofibers.