Flame Retardancy of Short Flax Fibers Modified by Radiation-Induced Grafting of Phosphonated Monomers: Comparison between Pre- and Simultaneous Irradiation Grafting.

Short flax fibers have been modified by radiation-induced grafting using methacrylate monomers containing phosphorus to give them a flame-retardant character. Two methodologies, namely pre-irradiation and simultaneous irradiation grafting, were examined. Certain parameters, notably the dose and the irradiation source (e-Beam and γ rays), were evaluated. The grafting efficiency, in terms of phosphorus content (mass percentage), was measured by X-ray fluorescence spectrometry (XRF). Using simultaneous irradiation, 2.39 wt% phosphorus could be obtained from 10 kGy, compared to 100 kGy in pre-irradiation. Furthermore, for similar phosphorus levels, the location of the grafted polymer chains was different for the two methodologies. The effect of phosphorus content on thermal properties and fire behavior was evaluated on a microscopic scale using a pyrolytic flow combustion calorimeter (PCFC) and on a laboratory scale using a cone calorimeter. It was then pointed out that flammability was linked to the phosphorus content and likely its location, which is associated with the radiation-induced grafting methodology, showing that the grafting conditions influence the final fire properties. Simultaneous irradiation, thus, proved to be more interesting in terms of efficiency and final properties.

Upgrading Pyrolytic Oil via Catalytic Co-Pyrolysis of Beechwood and Polystyrene.

This study aims to investigate the catalytic co-pyrolysis of beech wood with polystyrene as a synergic and catalytic effect on liquid oil production. For this purpose, a tubular semi-continuous reactor under an inert nitrogen atmosphere was used. Several zeolite catalysts were modified via incipient wetness impregnation using iron and/or nickel. The liquid oil recovered was analyzed using GC-MS for the identification of the liquid products, and GC-FID was used for their quantification. The effects of catalyst type, beechwood-to-polystyrene ratio, and operating temperature were investigated. The results showed that the Fe/Ni-ZSM-5 catalyst had the best deoxygenation capability. The derived oil was mainly constituted of aromatics of about 92 wt.% for the 1:1 mixture of beechwood and polystyrene, with a remarkably high heating value of around 39 MJ/kg compared to 18 MJ/kg for beechwood-based bio-oil. The liquid oil experienced a great reduction in oxygen content of about 92% for the polystyrene-beechwood 50-50 mixture in comparison to beechwood alone. The catalytic and synergetic effects were more realized for high beechwood percentages as a 75-25 beechwood-polystyrene mix. Regarding the temperature variation between 450 and 600 °C, the catalyst seemed to deactivate faster at higher temperatures, thus constituting a quality reduction in the pyrolytic oil in high-temperature ranges.

D2B-Functionalized Gold Nanoparticles: Promising Vehicles for Targeted Drug Delivery to Prostate Cancer.

Despite the multitude of therapeutic agents available to treat prostate cancer (PC), there are still no effective and safe measures to treat the tumor. It remains a challenge to develop a simple approach to target PC with specific antibodies. In our study, D2B monoclonal antibodies against a prostate-specific membrane antigen (PSMA) were used. We investigated the functionalization of gold nanoparticles (AuNPs) with D2B to generate favorable physicochemical and biological properties that mediate specific binding to PC. For this purpose, AuNPs with a size of about 25 nm were synthesized in water using sodium citrate as a reducing and stabilizing agent and then coated with D2B. Major physicochemical properties of naked and D2B-coated AuNPs were investigated by ultraviolet-visible (UV-vis) spectroscopy, dynamic light scattering (DLS), and zeta potential measurements. The successful binding of D2B to AuNPs-citrate caused a 15 nm red shift in the UV-vis. This was assessed by DLS as an increase in zeta potential from ∼-45 to ∼-23 mV and in the size of AuNPs from ∼25 to ∼63 nm. Scanning electron microscopy confirmed the size shift of AuNPs, which was detected as an exterior organic layer of D2Bs surrounding each AuNP. Even at high exposure levels of the bioconjugates, PSMA-PC-3 cells exhibited minimal cytotoxicity. The specific and dose-dependent binding of AuNPs-D2B to PC-3-PSMA cells was validated by flow cytometry analysis. Our data provide effective drug delivery systems in PC theranostics.

Influence of Polymer Processing on the Double Electrical Percolation Threshold in PLA/PCL/GNP Nanocomposites.

For the first time, the double electrical percolation threshold was obtained in polylactide (PLA)/polycaprolactone (PCL)/graphene nanoplatelet (GNP) composite systems, prepared by compression moulding and fused filament fabrication (FFF). Using scanning electron microscopy (SEM) and atomic force microscopy (AFM), the localisation of the GNP, as well as the morphology of PLA and PCL phases, were evaluated and correlated with the electrical conductivity results estimated by the four-point probe method electrical measurements. The solvent extraction method was used to confirm and quantify the co-continuity in these samples. At 10 wt.% of the GNP, compression-moulded samples possessed a wide co-continuity range, varying from PLA55/PCL45 to PLA70/PCL30. The best electrical conductivity results were found for compression-moulded and 3D-printed PLA65/PCL35/GNP that have the fully co-continuous structure, based on the experimental and theoretical findings. This composite owns the highest storage modulus and complex viscosity at low angular frequency range, according to the melt shear rheology. Moreover, it exhibited the highest char formation and polymers degrees of crystallinity after the thermal investigation by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. The effect of the GNP content, compression moulding time, and multiple twin-screw extrusion blending steps on the co-continuity were also evaluated. The results showed that increasing the GNP content decreased the continuity of the polymer phases. Therefore, this work concluded that polymer processing methods impact the electrical percolation threshold and that the 3D printing of polymer composites entails higher electrical resistance as compared to compression moulding.

Fabrication of PLA/PCL/Graphene Nanoplatelet (GNP) Electrically Conductive Circuit Using the Fused Filament Fabrication (FFF) 3D Printing Technique.

For the purpose of fabricating electrically conductive composites via the fused filament fabrication (FFF) technique whose properties were compared with injection-moulded properties, poly(lactic acid) (PLA) and polycaprolactone (PCL) were mixed with different contents of graphene nanoplatelets (GNP). The wettability, morphological, rheological, thermal, mechanical, and electrical properties of the 3D-printed samples were investigated. The microstructural images showed the selective localization of the GNPs in the PCL nodules that are dispersed in the PLA phase. The electrical resistivity results using the four-probes method revealed that the injection-moulded samples are insulators, whereas the 3D-printed samples featuring the same graphene content are semiconductors. Varying the printing raster angles also exerted an influence on the electrical conductivity results. The electrical percolation threshold was found to be lower than 15 wt.%, whereas the rheological percolation threshold was found to be lower than 10 wt.%. Furthermore, the 20 wt.% and 25 wt.% GNP composites were able to connect an electrical circuit. An increase in the Young's modulus was shown with the percentage of graphene. As a result, this work exhibited the potential of the FFF technique to fabricate biodegradable electrically conductive PLA-PCL-GNP composites that can be applicable in the electronic domain.

Novel Foaming-Agent Free Insulating Geopolymer Based on Industrial Fly Ash and Rice Husk.

This study highlights the synthesis of a new thermal insulating geopolymer based on the alkaline activation of fly ashes. A porous geopolymer material can be prepared without the addition of a foaming agent, using high ratio solution/ashes (activating solutions used are water, sodium or potassium hydroxide). In order to increase the porosity of the material and to make it more ecological, rice husks are incorporated into the formulation. The geopolymer materials were prepared at room temperature and dried at moderate temperature (105 °C) by a simple procedure. The microstructural characteristics of these new porous geopolymers were assessed by optical microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and X-ray fluorescence (XRF). Infrared spectroscopy (FTIR) was used to confirm the geopolymerisation. The effect of the ratio solution/ashes and the percentage of the rice husk addition on thermal and mechanical analysis was evaluated. An insulating material for a solution/ashes ratio of 0.9 and a rice husk content of 15% having a λ value of 0.087 W/(m·K), a porosity of 61.4% and an Rc value of 0.1 MPa was successfully prepared.

Fire Behavior of Thermally Thin Materials in Cone Calorimeter.

In this study, a representative set of thermally thin materials including various lignocellulosic and synthetic fabrics, dense wood, and polypropylene sheets were tested using a cone calorimeter at different heat fluxes. Time-to-ignition, critical heat flux, and peak of heat release rate (pHRR) were the main parameters considered. It appears that the flammability is firstly monitored by the sample weight. Especially, while the burning rate of thermally-thin materials does never reach a steady state in cone calorimeter, their pHRR appears to be mainly driven by the fire load (i.e., the product of sample weight and effective heat of combustion) with no or negligible influence of textile structure. A simple phenomenological model was proposed to calculate the pHRR taking into account only three parameters, namely heat flux, sample weight, and effective heat of combustion. The model allows predicting easily the peak of heat release rate, which is often considered as the main single property informing about the fire hazard. It also allows drawing some conclusions about the flame retardant strategies to reduce the pHRR..

Flame Retardant-Functionalized Cotton Cellulose Using Phosphonate-Based Ionic Liquids.

Cellulose from cotton fibers was functionalized through a dissolution-regeneration process with phosphonate-based ionic liquids (ILs): 1,3-dimethylimidazolium methylphosphonate [DIMIM][(MeO)(H)PO2] and 1-ethyl-3-methylimidazolium methylphoshonate [EMIM][(MeO)(H)PO2]. The chemical modification of cellulose occurred through a transesterification reaction between the methyl phosphonate function of ILs and the primary alcohol functions of cellulose. The resulting cellulose structure and the amount of grafted phosphorus were then investigated by X-ray diffraction, ICP-AES, and ¹³C and ³¹P NMR spectroscopy. Depending on the IL type and initial cotton / IL ratio in the solution, regenerated cellulose contained up to 4.5% of phosphorus. The rheological behavior of cotton cellulose/ILs solutions and the microscale fire performances of modified cellulose were studied in order to ultimately prepare flame retardant cellulosic materials. Significant improvement in the flame retardancy of regenerated cellulose was obtained with a reduction of THR values down to about 5-6 kJ/g and an increase of char up to about 35 wt%.

Sodium alginate adhesives as binders in wood fibers/textile waste fibers biocomposites for building insulation.

Alginate derived from seaweed is a natural polysaccharide able to form stable gel through carbohydrate functional groups largely used in the food and pharmaceutical industry. This article deals with the use of sodium alginate as an adhesive binder for wood fibres/textile waste fibres biocomposites. Several aldehyde-based crosslinking agents (glyoxal, glutaraldehyde) were compared for various wood/textile waste ratios (100/0, 50/50, 60/40, 70/30 and 0/100 in weight). The fully biomass derived composites whose properties are herewith described satisfy most of the appropriate requirements for building materials. They are insulating with a thermal conductivity in the range 0.078-0.089 W/m/K for an average density in the range 308-333 kg/m3 according to the biocomposite considered. They are semi-rigid with a maximal mechanical strength of 0.84 MPa under bending and 0.44 MPa under compression for 60/40 w/w wood/textile waste biocomposites with a glutaraldehyde crosslinking agent.

Effect of autohydrolysis of Miscanthus x giganteus on lignin structure and organosolv delignification.

The influence of the operating conditions of Miscanthus x Giganteus autohydrolysis on the composition of the solid residues and hydrolysates was examined. Milled wood lignin (MWL) extracted after autohydrolysis treatments performed at the same severity but at different temperatures were studied by (13)C and (31)P NMR in order to obtain a more complete picture of the changes in lignin structure occurring during the autohydrolysis. It was proposed that (1) the lignin homolytical fragmentation route should be enhanced with an increase of the temperature of the autohydrolysis treatment and (2) addition of a catalytic amount of 2-naphthol during the autohydrolysis step not only enhanced the dissolution of lignin but also allowed a better recovery of the hemicellulose sugars. A combined process involving an optimized autohydrolysis step (carried out in presence or not of 2-naphthol) and a low severity ethanol organosolv treatment was described for the separation and recovery of lignin, cellulose and hemicelluloses.