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.     

Processing and Morphology Impacts on Mechanical Properties of Fungal Based Biopolymer Composites

Fungal based biopolymer matrix composites with lignocellulosic agricultural waste as the filler are a viable alternative for some applications of synthetic polymers. This research provides insight into the impact of the processing method and composition of agriwaste/fungal biopolymer composites on structure and mechanical properties. The impact of nutrition during inoculation and after a homogenization step on the three-point bend flexural modulus and strength was determined. Increasing supplemental nutrition at inoculation had little effect on the overall composite strength or modulus; however, increasing carbohydrate loading after a homogenization step increased flexural stress at yield and bulk flexural modulus. The contiguity of the network formed was notably higher in the latter scenario, suggesting that the increase in modulus and strength of the final composite after homogenization was the result of contiguous hyphal network formation, which improves the integrity of the matrix and the ability to transfer load to the filler particles.     

Modification of Thermo-Mechanical Properties of Recycled PET by Vinyl Acetate (VAc) Monomer Grafting Using Gamma Irradiation

Vinyl acetate (VAc) monomer of different percentage was grafted onto the recycled polyethylene terephthalate (r-PET) films using gamma irradiation. The properties of these modified films were characterized by Fourier transform infrared spectroscopy (FTIR), mechanical properties testing (Tensile strength, Elongation at break), dynamic mechanical analysis (DMA) and thermo-gravimetric analysis (TGA). The Tensile Strength (TS) of the modified PET film increased by 132.25?% to the highest value of 50.12 MPa at 15% VAc monomer concentration at 3 kGy gamma dose, while the elongation at break (EB) decreased by 31.83?%. FTIR was used to investigate the molecular interaction of the modified films. TGA revealed that curve of the modified PET film shifted toward higher temperature region by 95?°C, which is very close to that of PET film made from virgin flakes. The results indicate that modified PET films of better mechanical and thermal properties were successfully prepared using VAc monomer grafting by gamma irradiation technique.     

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.     

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.     

Coupling of the Water Cycle with Patterns of Urban Growth in the Baltimore Metropolitan Region,United States

Regional municipal water plans typically do not recognize complex coupling patterns or that increased withdrawals in one location can result in changes in water availability in others. We investigated the interaction between urban growth and water availability in the Baltimore metropolitan region where urban growth has occurred beyond the reaches of municipal water systems into areas that rely on wells in low‐productivity Piedmont aquifers. We used the urban growth model SLEUTH and the hydrologic model ParFlow.CLM to evaluate this interaction with urban growth scenarios in 2007 and 2030. We found decreasing groundwater availability outside of the municipal water service area. Within the municipal service area we found zones of increasing storage resulting from increased urban growth, where reduced vegetation cover dominated the effect of urbanization on the hydrologic cycle. We also found areas of decreasing storage, where expanding impervious surfaces played a larger role. Although the magnitude of urban growth and change in water availability for the simulation period were generally small, there was considerable spatial heterogeneity of changes in subsurface storage. This suggests that there are locally concentrated areas of groundwater sensitivity to urban growth where water shortages could occur or where drying up of headwater streams would be more likely. The simulation approach presented here could be used to identify early warning indicators of future risk.     

Applying Statistical Causal Analyses to Agricultural Conservation: A Case Study Examining P Loss Impacts

Estimating the effect of agricultural conservation practices on reducing nutrient loss using observational data can be confounded by factors such as differing crop types and management practices. As we may not have the full knowledge of these confounding factors, conventional statistical meta‐analysis methods can be misleading. We discuss the use of two statistical causal analysis methods for quantifying the effects of water and soil conservation practices in reducing P loss from agricultural fields. With the propensity score method, a subset of data was used to form a treatment group and a control group with similar distributions of confounding factors. With the multilevel modeling method, data were stratified based on important confounding factors, and the conservation practice effect was evaluated for each stratum. Both methods resulted in similar estimates of the conservation practice effect (total P load reduction avg. ~70%). In addition, both methods show evidence of conservation practices reducing the incremental increase in total P export per unit increase in fertilizer application. These results are presented as examples of the types of outcomes provided by statistical causal analyses, not to provide definitive estimates of P loss reduction. The enhanced meta‐analysis methods presented within are applicable for improved assessment of agricultural practices and their effects and can be used for providing realistic parameter values for watershed‐scale modeling.     

The IPBES Conceptual Framework: An Unhelpful Start

The Intergovernmental Platform on Biodiversity and Ecosystem Services (IPBES) have recently launched themselves as the UN-sanctioned instrument for conserving nature. They seek to establish themselves as the authority in this field alongside the well-known Intergovernmental Panel on Climate Change in climate science. Quickly following or even before recent publication of their conceptual framework in two biology journals, they were already underway building upon it. This headlong push, we believe, is ill advised. We show how the framework is unsound as a foundation for further work—in a number of ways and perhaps even by its authors’ own lights. It is therefore urgent that the IPBES thoroughly and thoughtfully reconsider their framework before too much effort is wasted.     

Production of soybean ethanol-based biodiesel using CaO heterogeneous catalysts promoted by Zn,K and Mg

This article focuses on the optimization of the production of fatty acid ethyl esters from soybean oil using CaO-based heterogeneous catalysts. Three different catalytic promoters were evaluated: Magnesium, zinc, and potassium. The reaction has evaluated the promoter content (promoter to calcium molar ratio), catalyst load, alcohol to oil molar ratio, and temperature. Response surface methodology (RSM) was used to evaluate the influence of each variable on the yield of biodiesel. The addition of K₂O or MgO in the catalyst has enhanced the yield in fatty acid ethyl esters, while the use of ZnO as a promoter was not successful.     

The synergistic effect of air mass on outdoor performance for different PV module in India

The effect of air mass (AM) on the performance of multi-crystalline silicon (m-Si), amorphous silicon (a-Si), and hetero-junction with intrinsic thin layer (HIT)-technology-based photovoltaic (PV) modules are evaluated for representative day of four seasons during the year 2011 for composite climate of India. To find the best performing PV module technology with respect to AM at the site, annual energy yields and performance ratio against different AM bands (AM 1–4.5) are plotted. It is found that HIT modules perform better than m-Si and a-Si at each AM band. Annual energy yields for all three technologies decrease with increasing order of AM bands. The performance ratio for HIT and m-SI modules initially increases and then decreases with increasing order of AM bands. However, for a-Si modules, the performance ratio decreases with increasing order of the AM bands.