Man-Made and Natural Fibres as a Reinforcement in Fully Biodegradable Polymer Composites: A Concise Study

Biodegradable and ecologically friendly polymer materials attract great attention of many scientific groups in the world as they fit well in the sustainable development policy and are considered to be “a right thing to do” by the general public. Such polymers can be modified by the addition of different fillers, favorably of natural origin. In the paper we provide a comparison between composites based on two biodegradable polymers: poly(lactic acid)—biodegradable, natural stock polymer and poly(butylene succinate)—biodegradable polymer produced from fossil based materials. For each polymer we have prepared a series of composites with different fibres (natural: hemp and flax, and manmade: Cordenka) and different filler loadings. To fully characterize obtained materials thermal, mechanical and surface free energy measurements were performed, completed with morphology observations and an attempt to compare the experimental data for tensile measurements with values obtained using the modified rule of mixtures. The tensile results calculated using the modified rule of mixture for below 30% fibre loading are found to be fitting the experimental data. Composites mechanical properties and morphology were strongly affected by the type of fibre used and its loading, however thermal properties remained almost unchanged. In specific, Cordenka fibres tend to form bunches which presence greatly influences the mechanical properties but still our studies have shown clear advantage of manmade Cordenka fibres over the hemp and flax fibres when considering distribution and fibre–polymer interaction.     

A Solvent-Free Approach for Production of Films from Pectin and Fungal Biomass

Self-binding ability of the pectin molecules was used to produce pectin films using the compression molding technique, as an alternative method to the high energy-demanding and solvent-using casting technique. Moreover, incorporation of fungal biomass and its effects on the properties of the films was studied. Pectin powder plasticized with 30% glycerol was subjected to heat compression molding (120 °C, 1.33 MPa, 10 min) yielding pectin films with tensile strength and elongation at break of 15.7 MPa and 5.5%, respectively. The filamentous fungus Rhizopus oryzae was cultivated using the water-soluble nutrients obtained from citrus waste and yielded a biomass containing 31% proteins and 20% lipids. Comparatively, the same strain was cultivated in a semi-synthetic medium resulting in a biomass with higher protein (60%) and lower lipid content (10%). SEM images showed addition of biomass yielded films with less debris compared to the pectin films. Incorporation of the low protein content biomass up to 15% did not significantly reduce the mechanical strength of the pectin films. In contrast, addition of protein-rich biomass (up to 20%) enhanced the tensile strength of the films (16.1–19.3 MPa). Lastly, the fungal biomass reduced the water vapor permeability of the pectin films.     

Photo-Stabilisation and UV Blocking Efficacy of Coated Macro and Nano-Rutile Titanium Dioxide Particles in Paints and Coatings

Surface treated macro and nanoparticle TiO₂ samples have been prepared, characterised and their efficiency as UV blockers evaluated in clear coatings and paints. The particle size of the ‘base’ TiO₂ has been optimised to block UV radiation and the surface treatment developed to deactivate the photocatalytic activity of the surface of the TiO₂ particles. The resultant UV blockers have been evaluated in both solvent and water-based clear coatings. Nanoparticle TiO₂ has been prepared from ‘seed’ and the particle size was controlled by calcination. It was found that the choice of particle size is a compromise between UVA absorption, UVB absorption, visible transmission and photoactivity. It has been demonstrated that TiO₂ with a crystallite size of 25 nm yields a product with the optimum properties. A range of dispersants was successfully used to disperse and mill the TiO₂. Both organic and inorganic dispersants were used; 2-amino-2-methyl-1-propanol and 1-amino-2-propanol (MIPA) and P₂O₅ and Na₂SiO₃ respectively. The surface of the nano-TiO₂ was coated with mixed oxides of silicon, aluminium, zirconium and phosphorous. Addition of the resultant coated nano-rutiles to an Isocyanate Acrylic clear coating prolonged the lifetime of that coating compared to the blank. Generally, a surface treatment based on SiO₂, Al₂O₃ and P₂O₅ was more successful than one based on ZrO₂, Al₂O₃ and P₂O₅. Higher addition levels of the surface treatment were beneficial for protecting the polymeric coating. The UV blocker products were also evaluated in a water-based acrylic, first a water-based dispersion of the UV blocker was prepared before addition to the acrylic. The dispersions and resultant acrylic thin films were evaluated using UV/Vis spectroscopy and durability assessed. The ratio of absorbance at 300:500 nm for the water-based dispersion was shown to be a good predictor of both the transparency of the resultant acrylic thin film and the durability of that film, in terms of weight loss. Macro grade titanium dioxide pigments were also prepared and coated with treatments of silica, alumina and siloxane and their photo-stabilising activity in alkyd paint film assessed and found to be directly related to the electron–hole pair mobility and trapping as determined by micro-wave spectroscopy.     

Utilization of Waste Lignin and Hydrolysate From Chromium Tanned Waste in Blends of Hot-Melt Extruded PVA-Starch

The demand for biodegradable plastic material is increasing worldwide. However, the cost remains high in comparison with common forms of plastic. Requirements comprise low cost, good UV-stability and mechanical properties, as well as solubility and water uptake lead to the preparation of multi-component polymer blends based on polyvinyl alcohol and starch in combination with waste products that are hard to utilize—waste lignin and hydrolysate extracted from chromium tanned waste. Surprisingly the addition of such waste products into PVA gives rise to blends with better biodegradability than commercial PVA in an aquatic aerobic environment with non-adapted activated sludge. These blends also exhibited greater solubility in the water and UV stability than commercial PVA. Tests on the processing properties of the blends (melt flow index, tensile strength and elongation at break of the films) as well as their mechanical properties showed that materials based on these blends might be applied in agriculture (for example as the systems for controlled-release pesticide or fertilizer) and, somewhat, in the packaging sector.     

Interactive Influence of Biofiber Composition and Elastomer on Physico-Mechanical Properties of PLA Green Composites

The objective of this work was to improve the impact and thermal properties of polylactic acid (PLA)-based biocomposite by appropriate application of cellulosic fiber and a bioelastomer. Biocomposites formulations with fiber contents of up to 20% in combination with a bioelastomer were extrusion-compounded in a twin-screw extruder followed by molding in an injection molding system. Fibers used in the formulations included three types of cellulosic fiber; namely, raw fiber from oat hull biomass (RF), hydrolysis byproduct (ATF) which was the solid fraction obtained from an acid-catalyzed hydrolysis of RF, and delignified fibers (AD30, AD65, AD100) which were the products of delignification of ATF. Formulated biocomposites were characterized for thermal (glass transition and melting temperatures, and enthalpy of melting) and physico-mechanical (tensile and bending strengths, stiffness, impact energy, and water absorption) properties. Among all types of biofibers, RF resulted in poor properties in the biocomposites due to the high hemicellulose content in the structure. On the other hand, the ratio of lignin to cellulose (in the absence of hemicellulose) in the modified fibers did not significantly affect the physico-mechanical and thermal properties of the biocomposites. The elastomer applied in the formulations improved the impact energy, thermal properties, and elongation at break of the composites. However, it adversely affected the strength and water resistance of biocomposites, especially in the presence of hemicellulose. The results indicated that, depending on the application, a wide range of PLA green composites with different physico-mechanical properties can be achieved.     

Performance of Cow Dung Reinforced Biodegradable Poly(Lactic Acid) Biocomposites for Structural Applications

In this work, performance of cow dung (CD) reinforced poly(lactic acid) (PLA) biocomposites was investigated for the potential use in load bearing application. CD of average 4 mm size was blended with PLA at different CD ratios (0–50 wt%) and their effects on the biocomposite properties were studied. The results showed an improvement in the flexural properties, while the tensile and impact strength dropped by 20 and 28% with the addition of 50% CD. The decline in the tensile and impact strength was due to micro-cracking and voids formation at higher CD content. Also, the incorporation of CD slightly decreased the thermal stability of the biocomposite. However, dynamic mechanical properties of the biocomposites generally improved. SEM analysis of tensile and impact fractured surfaces indicated that the CD had a reasonable adhesion with matrix. Moreover, the SEM micrographs of soil burial studies showed an accelerated degradation of higher CD wt% biocomposites.     

A Comparative Study of Doum fiber and Shrimp Chitin Based Reinforced Low Density Polyethylene Biocomposites

The aim of this paper was to study the effects of reinforcing low density polyethylene (LDPE) by using bio-fillers (Doum cellulose or Shrimp chitin) on the mechanical properties. Both, Doum cellulose extracted frsom Doum leaves and Shrimp chitin extracted from shrimp co-products were compounded with LPDE without and with compatibilizer. The biocomposites were prepared by melt blending in a twin-screw extruder. Torsion and flexural tests were performed to investigate the impact of each reinforcement on the biocomposite mechanical properties. The SEM was carried out to study the filler/polymer interface adhesion. The present study has demonstrated that Doum fibers and shrimp chitin succeed in improving the mechanical properties of LPDE bio-composites. The results also showed that the use of maleic anhydride-grafted polyethylene as a compatibilizer improves filler adhesion/matrix and mechanical properties. This study exhibits that polyethylene composites based on Doum fibers or shrimp chitin can be used to replace the polyethylene materials in several fields like packaging and automotive industries.     

One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials

The use of petroleum-derived products should be avoided regarding the principles of green and sustainable chemistry. The work reported herein, is aimed at the liquefaction of pine shavings for the production of an environmentally-friendly polyol suitable to be used in the formulations of sprayable polyurethane foams. The biopolyols were obtained in high yield and were used to replace those derived from fossil sources, to produce more “greener” polyurethane foams and therefore, less dependent on petroleum sources, since the polyol component was substituted by products resulting from biomass liquefaction. The partial and fully exchange of the polyols was accomplished, and the results compared with a reference foam. The foams were afterward, chemical, physical, morphological, and mechanically characterized. The complete replacement of polyether polyol and polyol polyester has presented some similar characteristics as that used as a reference, validating that the path chosen for the development of more sustainable materials is on the right track for the contribution to a cleaner world.     

Biodegradation of Poly(Aspartic Acid-Itaconic Acid) Copolymers by Miscellaneous Microbes from Natural Water

Poly(aspartic acid-itaconic acid) copolymers (PAI) is a new scale inhibitor for water treatment. Thus, it is necessary to investigate its biodegradability. The biodegradability of PAI was investigated through CO₂ evolution tests under different conditions based on determination of carbon dioxide production. The investigation results showed that the degradation rate of PAI on day 10 and day 28 were respectively 38.7 and 79.5%, indicating that PAI was one kind of easily biodegradable scale inhibitors. With the increase in the content of itaconic acid in copolymerization process, the biodegradability of PAI was significantly reduced. In addition, the high biodegradability might be attributed to the existence of C–N bone-structure and more –COO–. Finally, Cu²⁺ could decrease the degradation percentage and the enzyme inhibition effect of Cu²⁺ was not the linear effect, but the “low-dosage effect”.     

Effects of Compounded Curing Agents on Properties and Performance of Urea Formaldehyde Resin

The effects of three compounded curing agents on the properties and performance of the urea-formaldehyde (UF) resin were investigated in this study. The compounded curing agents were prepared by mixing ammonium chloride with hexamethylenetetramine, citric acid, and oxalic acid respectively at a ratio of 1:1, named N-H, N–CA, and N–OA, respectively. The curing process, crystallinity, and physical properties were measured, and the three-ply plywood was fabricated to measure its prepress strength, wet shear strength, and formaldehyde emission. Results showed that the compounded curing agents N–CA and N–OA enhanced the initial viscosity, crosslinking density and thermal stability of UF resin. Additionally, the prepress strength of the plywood bonded by UF resin with N–CA and N–OA increased by 82 and 111% respectively compared to the UF resin with NH₄Cl, and the wet shear strength increased by 14 and 16%, the formaldehyde emission decreased by 19 and 42% respectively. However, owing to the short pot-life of these curing agent limited their storage time, the curing agents N–CA and N–OA should be applied to fabricate plywood in winter for obtaining a better bond strength and a lower formaldehyde emission. While the UF resin with N–HT showed a suitable pot-life, so it could be applied to fabricate plywood in summer for long time storage and avoiding procuring problem.