Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M _n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by ¹H NMR, quantitative ¹³C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.     

Modelling and Optimization of Uranium (VI) Ions Adsorption Onto Nano-ZnO/Chitosan Bio-composite Beads with Response Surface Methodology (RSM)

Nano-ZnO-chitosan bio-composite beads were prepared for the sorption of \({\text{UO}}_{2}^{{2+}}\) from aqueous media. The resulting nano-ZnO/CTS bio-composite beads were characterized by TEM, XRD etc. The sorption of \({\text{UO}}_{2}^{{2+}}\) by bio-composite beads was optimized using RSM. The correlation between four variables was modelled and studied. According to RSM data, correlation coefficients (R²?=?0.99) and probability F-values (F?=?2.24?×?10^??10) show that the model fits the experimental data well. Adsorption capacity for nano-ZnO/CTS bio-composite beads was obtained at 148.7 mg/g under optimum conditions. The results indicate that nano-ZnO/CTS bio-composite beads are appropriate for the adsorption of \({\text{UO}}_{2}^{{2+}}\) ions from aqueous media. Also, the suitability of adsorption values to adsorption isotherms was researched and thermodynamic data were calculated.     

Fabrication of Admicelled Natural Rubber by Polycaprolactone for Toughening Poly(lactic acid)

Natural rubber (NR) with polycaprolactone (PCL) core–shell (NR-ad-PCL), synthesized by admicellar polymerization, was acted as an impact modifier for poly(lactic acid) (PLA). PLA and NR-ad-PCL were melt-blended using a co-rotating twin screw extruder. The morphology of PLA/NR-ad-PCL blends showed good adhesion as smooth boundary around rubber particles and PLA matrix. Only 5 wt% of rubber phase, NR-ad-PCL was more effective than NR to enhance toughness and mechanical properties of PLA. The contents of the NR-ad-PCL were varied from 5, 10, 15 and 20 wt%. From thermal results, the incorporation of the NR-ad-PCL decreased the glass transition temperature and slightly increased degree of crystallinity of PLA. Mechanical properties of the PLA/NR-ad-PCL blends were investigated by dynamic mechanical analyser, pendulum impact tester and universal testing machine for tension and flexural properties. The increasing NR-ad-PCL contents led to decreasing Young’s and storage moduli but increasing loss modulus. Impact strength and elongation at break of the PLA/NR-ad-PCL blends increased with increasing NR-ad-PCL content up to 15 wt% where the maximum impact strength was about three times higher than that of pure PLA and the elongation at break increased to 79%.     

Biopolymer (Chitin) from Various Marine Seashell Wastes: Isolation and Characterization

Chitin has been produced from different sea waste sources including, molluscs (mussel and oyster shell), crustacean (prawn and crab) and fish scale (pang and silver scales) using deproteinization and demineralization as chemical methods. The conditions of chemical extraction process determine the quality of chitin. The obtained results revealed that, about 1 and 10% HCl and NaOH were adequate concentrations for deproteinization and demineralization process respectively. Chitin from oyster and crab shell waste had the highest yield of 69.65 and 60.00% while prawn, mussel shell, pang and silver scales had the lowest yield of 40.89, 35.03, 35.07 and 31.11% respectively. Chitin solubility is controlled by the quantity of protonated acetyl groups within the polymeric chain of the chitin backbone, thus on the percentage of acetylated and non-acetylated d-glucos-acetamide unit. Good solubility results were obtained in mussel, oyster and crab shells respectively. The chitin molecular weight characteristics and activity are controlled by the degree of acetylation (DA) and the distribution of acetyl group extending in the polymer chain. DA is determined by acid-base titration methods and molecular weight determined by Brookfield viscometry. Both methods are found to be effective.     

Sustainable Use of Coffee Husks For Reinforcing Polyethylene Composites

The utilization of the coffee husk fiber (CHF) from the coffee industry as a reinforcing filler in the preparation of a cost-effective thermoplastic based composite was explored in this study. The chemical composition and thermal properties of the CHF were investigated and compared with those of wood fiber (WF). CHF proved to be mainly composed of cellulose, hemicellulose and lignin, and exhibited similar thermal behavior to WF. High density polyethylene (HDPE) composites with CHF loadings of from 40 to 70% were prepared using melt processing and extrusion. The processing properties, mechanical behavior, water absorption and thermal performance of these composites were investigated. The effect of maleated polyethylene (MAPE) used as a coupling agent on the composite was explored. The experimental results showed that increasing the CHF loading in the HDPE matrix resulted in an increase in the modulus and thermal properties of the composites, but resulted in poor water resistance. The addition of a 4% MAPE significantly improved the interfacial behavior of the hydrophilic lignocellulosic fiber and the hydrophobic polymer matrix.     

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.     

Production of Curdlan Grown on Cassava Starch Waste Hydrolysates

Cassava starch waste hydrolysates (CSWHs) with different degrees of polymerisation, i.e., CSWHs-1, CSWHs-2 and CSWHs-3, were prepared through the hydrolysis of cassava starch waste with thermostable a-amylase from Thermococcus sp. HJ21. The prepared CSWHs were then used as a carbon source for curdlan production with Alcaligenes faecalis ATCC 31749. The amount of curdlan produced and the glucosyltransferase activity during curdlan synthesis increased more obviously when CSWHs-2 was used as the carbon source than when glucose was used. Using both carbon sources, the maximum curdlan production was observed at day 5, and the maximum glucosyltransferase activity was observed at day 4. Glucosyltransferase activity decreased thereafter, and biomass continued to increase until the end of the experiment (day 6). Results indicated that the enhanced curdlan production with CSWHs as the carbon source was highly correlated with glucosyltransferase activity.     

Thermally Stable Pyrolytic Biocarbon as an Effective and Sustainable Reinforcing Filler for Polyamide Bio-composites Fabrication

Natural fibers are limited in their use as reinforcement to commodity polymers. They cannot be used to reinforce engineering polymers due to their low thermal stability at high processing temperatures. This study presents an approach to successfully reinforce polyamides using a derivative of natural fibers as reinforcement without the effects of thermal degradation during melt processing. Biocarbon from miscanthus fibers was used to reinforce polyamide 6 up to 40 wt%. At 40 wt% filler content, the tensile and flexural strengths increased by 19.6 and 47% respectively in comparison to the neat polyamide. The moduli were also increased by 31.5 and 63.7% respectively. A maximum increase in impact strength of 43.7% was achieved at 20 wt% biocarbon loading. The morphology of the tensile fractured samples showed stretched polyamide ligaments attached to the biocarbon particles, indicating the presence of interaction between filler and matrix. Interestingly, more bonded interfaces were observed between the polyamide and biocarbon particles with increasing biocarbon content possibly stemming from increased biocarbon surfaces with functional groups. These composites show great potential to substitute in part or whole, some particulate filled polyamides currently used in the automotive industry.     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.     

Preparation and Characterization of Xylan Derivatives and Their Blends

Although hemicellulose is found widely in nature, it is currently under-utilized as a raw material for commercial applications. It would be desirable to find new uses for hemicellulose in order to add value to this agro-based material. A common type of hemicellulose is xylan, which is found in a number of wood species and in cotton. In this work we prepared cationic and anionic xylan derivatives and characterized them by ¹³C NMR, FT-IR, size exclusion chromatography (SEC), thermal analysis, and rheology. In particular, the ¹³C NMR spectra of carboxymethyl xylan (CMX) and quaternary ammonium-adducted xylan (QAX) were fully assigned with the help of samples with different degrees of substitution. SEC indicated that the beechwood xylan showed a bimodal molecular weight distribution, but with derivatization the distribution tended to become unimodal. Thermal analysis and rheology studies did not uncover any surprises; the solution of xylan and its derivatives exhibited mostly Newtonian behavior. The blends of CMX and QAX produced a precipitate at almost all ratios, indicating the formation of a polyelectrolyte complex. When cationic and anionic xylan samples were added together to paper, the paper dry strength increased. Thus, the combination of cationic/anionic xylan may be of interest in selected applications.