Microwave Assisted Synthesis of Urethane Modified Polyesteramide Coatings from Jatropha Seed Oil

In this study, we have developed urethane modified polyesteramide (UPEA) resin by the condensation polymerization reaction of N,N-bis (2-hydroxy ethyl) jatropha oil fatty amide (HEJA) and itaconic acid to form polyesteramide (PEA). The latter was further reacted with different percentages (16–22%) of toluylene 2,4-diisocyanate (TDI) to prepare UPEA. The structural elucidation of HEJA, PEA, UPEA was carried out by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The coating was made on mild steel strips. The physico-chemical and physico-mechanical analyses were carried out by standard laboratory methods. The thermal stability of polymer was studied by thermogravimetric analysis. Thermal analyses shows that these coatings can be used safely up to 230 °C. The corrosion protective behavior of UPEA coatings was investigated in acid, alkali, water and xylene. All the coatings exhibited good chemical resistance performance in acid, alkali, saline and organic solvents, while the resin UPEA 20 showed the best performance.     

Development of Anticorrosive Poly(Ether-Urethane) Amide Coatings from Linseed Oil: A Sustainable Resource

Polyetheramide(PEtA) resin was synthesized by the condensation polymerization of N,N-bis(2-hydroxy ethyl) linseed oil fatty amide diol (HELA) with resorcinol. It was further treated with different percentage of toluylene 2-4-diisocyanate (TDI) to obtain the urethane modified polyetheramide resins (UPEtA). The structural elucidation of PEtA and urethane modified polyetheramide(UPEtA) were carried out by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. These analyses confirm the formation of PEtA and UPEtA. Physico-chemical and physico-mechanical analysis were performed by standard laboratory methods. The resin composition UPEtA-24 showed best physico-mechanical properties with scratch hardness 2.0 kg, impact resistance 150 lb/in. and good bending ability. The thermal stability and curing behavior of polymers were respectively studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal analysis shows that these coatings can be used safely upto 190 °C. The coatings of UPEtA resins were prepared on mild steel strips. The anticorrosive behavior of UPEtA coatings were investigated in acid, alkali, water and xylene. All the coatings exhibit good chemical resistance performance in acid, alkali, saline and organic solvents, while the resin UPEtA-24 shows the best performance.     

Influence of Carbonyl Fe on Degradation of Epoxy in Ozone Environment

Carbonyl iron/epoxy coatings are widely used in military as a radar absorbing coating (RAC). The behaviors of RACs under working environments are very important, especially in the new environments such as ozone appeared with widening of the application fields. The effects of ozone degradation on pure epoxy cured with anhydride and the influence of carbonyl Fe on the degradation of epoxy are studied. The results indicate that if the peak at 1,510 cm⁻¹ was used as the inner standard, the intensity of absorption peaks at 1,738, 1,247 and 1,182 cm⁻¹ increases with exposure time for pure epoxy resin, while for the carbonyl iron/epoxy coatings, the three peaks changes insignificantly with the exposure time. The results indicates the oxidation process begins at the hydroxyl and methyl groups, and finally ozonide and carbonyl are formed on the surface for pure epoxy, and epoxy is eroded gradually in depth by ozone. Carbonyl iron could hinder the meeting of ozone with epoxy with dilution or hindrance effect and could protect epoxy resin from ozone and thus delay the deterioration of the coating performance.     

Development of Ambient Cured Polyesteramide Coatings from Linseed Oil: a Sustainable Resource

The resourceful employment of vegetable oil based polymers in coating applications that yield novel properties, faces challenges usually in their processing. We have developed polyesteramide coatings from linseed (Linnum ussitatissium seeds) oil with improved coating properties. Linseed oil was first converted into N, N-bis 2-hydroxy ethyl linseed oil fatty amide diol (HELA). The resin was synthesized by the reaction of HELA with ethylenediaminetetraacetic acid (EDTA) to develop ethylenediamine polyesteramide (Ed-PEA). The latter was further treated with poly (styrene co-maleic anhydride) (SMA) in different (35–50) phr (part per hundred part of resin) to obtain ambient cured polyesteramide (AC-PEA). The structural elucidation of polymeric resin (AC-PEA) was carried out by FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopic techniques. Thermal behavior of AC-PEA was studied by thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC). The coatings of AC-PEA were prepared on mild steel strips to investigate their physico-mechanical and anticorrosive behavior (in acid, alkali, water and xylene). It was found that among all the samples, the one having 45 phr of SMA showed the best physico-mechanical and corrosion resistance performance. The thermal stability performance suggests that AC-PEA45 system could be safely used up to 150 °C.     

Palm Oleic Acid Based Alkyds: Effect of the Fatty Acid Content on the Polyesterification Kinetics

The kinetic behavior of polyesterification of the alkyd resins synthesized using glycerol and phthalic anhydride modified with oleic acid from the palm oil at temperatures between 120 and 240 °C was studied. Three alkyds having oleic acid contents of 28, 40, and 65% were prepared by employing fatty acid method. The extent of the polyesterification reaction and average degree of polymerization were monitored by determining the acid number of the aliquot of the reaction mixture at various intervals of time and by measuring the volume of water evolved. Kinetic studies revealed that initial reaction rates followed a second-order kinetics up to certain limit and thereafter deviations were observed. The extent of reaction varied from 77.4 to 86.3% before deviation for all the three samples and exhibited a considerable degree of conversion. The second-order rate constants calculated from the linear part were found to be of the order of 10⁻⁵ g (mg KOH)⁻¹ min⁻¹. Molecular weight of the alkyd samples was determined by GPC; number average molecular weight of the alkyds ranged from 980 to 2,070.     

Adhesive Performance of Sorghum Protein Extracted from Sorghum DDGS and Flour

Distillers dried grains with solubles (DDGS) is the main co-product from grain-based ethanol production. The objective of this research was to compare the adhesive performance of three types of sorghum proteins: acetic acid-extracted sorghum protein from DDGS (PI), aqueous ethanol-extracted sorghum protein from DDGS (PII) and acetic acid-extracted sorghum protein from sorghum flour (PF). Physicochemical properties including amino acid composition, and rheological, thermal and morphological properties also were characterized. Results showed that PI had the best adhesion performance in terms of dry, wet and soak adhesion strength, followed by PF and PII. The wet strength of PI at a concentration of 12% protein assembled at 150 °C was 3.15 MPa, compared to 2.17 MPa and 2.59 MPa for PII and PF, respectively. DSC thermograms indicated that the PF protein isolates contained higher levels of carbohydrates than PI and PII; such non-protein contaminants in the PF isolate could be the reason for its lower adhesion strength than PI. In addition, PI might have more hydrophobic amino acids aligned at the protein-wood interface than PII, which could explain the better water resistance of PI. The optimum sorghum protein concentration and pressing temperature for maximum adhesion strength was 12% and 150 °C. PI had a significantly higher wet strength (3.15 MPa) than unmodified soy protein (1.63 MPa for soy protein). The high percentage of hydrophobic amino acids in PI (57%) was likely a key factor in the increased water resistance of PI compared with soy protein (36% hydrophobic amino acids). These results indicated that sorghum protein has huge potential as an alternative to petroleum-based adhesives.     

Performance and suitability of a landfill bioreactor with low cost biofilm contained clay-waste polyethylene-clay composite liner system for tropical climates of Asian countries

The objective of the study was to develop a low cost and environmentally friendly liner system for a landfill bioreactor to harness energy from waste. The landfill bioreactor test cell was constructed and evaluated for performance under dry tropical conditions of Sri Lanka. The research was carried out from March 2009 to September 2010. The clay-waste polyethylene-clay composite liner system was developed and permeability was tested. The permeability values of the liner under both saturated and unsaturated conditions at the high estimated hydraulic head of 86.2 cm were in between 6.3 × 10⁻⁸ and 2.6 × 10⁻⁸ cm/s. The permeability of the liner under waste filled condition varied between 2.17 × 10⁻⁹ and 8.15 × 10⁻⁹ cm/s, which satisfies the standard permeability value. Thus, the results were below the minimum requirement at very high estimated leachate head. After loading the test cell, leachate and permeate characteristics were analyzed for 273 days, from January 2010 to September 2010. The study showed the relationships among various parameters including pH, electrical permeability, chemical oxygen demand, biological oxygen demand, ammonia, nitrate, phosphate, total solids, volatile solids, total suspended solids and volatile suspended solids. The results of the analysis indicated that there are significant differences in the values of leachate and permeate parameters. The permeate parameters had values very much lower than those of leachate. It reveals that the clay-waste polyethylene-clay composite liner system reduced the concentration of these parameters when the leachate passed through the liner. The biofilm formed in waste polyethylene within the liner may have degraded most of organic materials found in the leachate when it passed through the liner. Therefore, the clay-waste polyethylene-clay composite liner system can be applied for full scale landfill bioreactors, particularly for Asian developing countries, due to better performance and more environmentally friendly characteristics.     

Thermo-chemical extraction of fuel oil from waste lubricating grease

This study investigated the recovery of oil from waste grease through the process of thermal degradation in an aqueous solution of potassium hydroxide (KOH) followed by solvent extraction. Waste high temperature metal bearing grease was dissolved in a 15 w/w% KOH solution at 80 °C while being agitated at 2000 rpm using a shear action agitator for a period of 15 min. Two distinct layers were observed after 8 min of settling time. The top layer being of dark brown oil and the bottom layer was a heterogeneous mixture. The two layers were separated by decantation. The bottom layer was cooled down to 45 °C followed by slow addition of toluene (C₇H₈) while agitating at 1200 rpm for 15 min to prevent solids settling and minimise rapid volatilisation of the organic compounds in the mixture. Two distinct layers were also formed, the top homogeneous mixture of light brown oil–toluene mixture and the bottom sludge layer. The solvent was recovered from the oil for re-use by fractional distillation of the homogenous mixture. It was observed that 15 w/w% potassium hydroxide solution can chemically degrade the soap matrix in the grease and extract up to 49 w/w% of the fuel oil when subjected to high shear stress at a temperature of 80 °C. The 26 w/w% extraction of oil in the remaining sludge was obtained by solvent extraction process with mass ratios of sludge to solvent of 2:1. Solvent recovery of 88% by mass was obtained via fractional distillation method. The combined extraction processes brought an overall oil yield of 75 w/w% from the waste grease. The fuel oil obtained from this process has similar properties to paraffin oil and can be blended with other oils as an alternative energy source.     

Batchwise mesophilic anaerobic co-digestion of secondary sludge from pulp and paper industry and municipal sewage sludge

Residues from forest-industry wastewater-treatment systems are treated as waste at many pulp and paper mills. These organic substances have previously been shown to have potential for production of large quantities of biogas. There is concern, however, that the process would require expensive equipment because of the slow degradation of these substances. Pure non-fibrous sludge from forest industry showed lower specific methane production during mesophilic digestion for 19 days, 53 ± 26 Nml/g of volatile solids as compared to municipal sewage sludge, 84 ± 24 Nml/g of volatile solids. This paper explores the possibility of using anaerobic co-digestion with municipal sewage sludge to enhance the potential of methane production from secondary sludge from a pulp and paper mill. It was seen in a batch anaerobic-digestion operation of 19 days that the specific methane production remained largely the same for municipal sewage sludge when up to 50% of the volatile solids were replaced with forest-industry secondary sludge. It was also shown that the solid residue from anaerobic digestion of the forest-industry sludge should be of suitable quality to use for improving soil quality on lands that are not used for food production.     

Effects of Preparation Parameters on Properties of Soy Protein-Based Fiberboard

The effects of manufacturing parameters on mechanical properties of medium density fibreboard (MDF) bonded with modified soy protein-based glue were studied to find an appropriate manufacture technology. Physical properties of MDF made with different amount of wax emulsion were measured. Results indicated that water repellent had no obvious influence on physical properties of soy protein-based MDF boards. The fiberboards bonded with soy protein-based glue showed stronger water resistance properties than those bonded with urea–formaldehyde (UF) resins. Furthermore, the soy protein-based MDF boards had good quality [25.2% 24 h soak thickness swell (TS), 29.9 MPa modulus of rupture (MOR), 3130 MPa modulus of elasticity (MOE)], which met requirements of Chinese national standard. Practical processing parameters were obtained by orthogonal experiment, i.e., glue content 8.0%, hot-press temperature 200 °C, and hot-press time 150 s.     

Thermal and thermo-chemical pre-treatment of four waste residues and the effect on acetic acid production and methane synthesis

In this study four diverse solid waste substrates (coal, Kraft pulp solids, chicken feathers and chicken processing waste) were thermally pre-treated (70, 140 and 200 °C), under an inert (nitrogen) or oxidative (oxygen) atmosphere, and then anaerobically digested. Membrane inlet mass spectrometry during the thermal and thermo-chemical reactions was successfully used to establish oxygen and carbon dioxide gas fluxes and product formation (acetic acid). There was significant solids hydrolysis pre-treatment at 200 °C under an oxidative atmosphere, as indicated by a decrease in the volatile suspended solids and an increase in dissolved organic carbon. Greater concentrations of volatile fatty acids were produced under oxidative conditions at higher temperatures. The methane yield more than tripled for feathers after pre-treatment at 140 °C (under both atmospheres), but decreased after oxidative pre-treatment at 200 °C, due to the destruction of available carbon by the thermo-chemical reaction. Methane yield more than doubled for the Kraft pulp solids with the 200 °C pre-treatment under oxidative conditions. This study illustrated the power of wet oxidation for solids destruction and its potential to improve methane yields generated during anaerobic digestion.     

Distribution of copper,silver and gold during thermal treatment with brominated flame retardants

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition.In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.     

Applying the Protective Role of Condensed Tannins to Acrylic-based Surface Coatings Exposed to Accelerated Weathering

Condensed tannins, extractable from tree bark have been assessed as functional additives to provide a protective role to acrylic-based coating resins. In addition to retaining high antioxidant capacity, the UV absorption properties of native and chemically modified tannins were found to be variously impacted by pH and degree of esterification or etherification. When added to acrylic-based coatings, these tannins were found to contribute colour to a white-base, but only small perceptive differences were found for clear coated wood using typical additive loadings of 0.1–0.4%. Integration of tannins in native or modified form to do not inhibit the cure of acrylic coatings or found to leach from cured coating films. Accelerated weathering was used to evaluate the photo-stability of tannin-modified acrylic and styrene-acrylic coatings. Native and modified tannins with maleate or methylcarboxylate groups retaining high antioxidant activity were associated with significantly greater coating longevity and performance than use of a synthetic photostabiliser. Moreover, esterified condensed tannins with a high degree of substitution also outperformed synthetic additives indicating the inherent UV absorption potential of these materials also contributed this efficacy within the acrylic and styrene-acrylic coating systems.     

Synthesis of Alkyd Resin from Non-Edible Jatropha Seed Oil

The kinetics of polyesterification of glycerol, phthalic anhydride and jatropha oil leading to the formation of alkyd resins were studied. A series of alkyd resins having different amount of jatropha oil viz., 40–80% have been prepared by employing two stage alcoholysis-polyesterification process. The extent of reaction and average degree of polymerisation were calculated from the end group analysis of the reaction mixture withdrawn at regular intervals of time. The initial reaction rates followed the second order kinetics and thereafter deviations were observed. An appreciable degree of conversion was noticed from the extent of the reaction which lies in the range of 49.5–62.5%. The average degree of polymerisation calculated in the region of deviation from second order suggested the occurrence of chain branching at relatively shorter intervals along the polymer chain. The second order rate constants were found to be of the order of 10⁻⁵ g (mg KOH)⁻¹ min⁻¹.     

<Emphasis Type="Italic">Mesua ferrea</Emphasis> L. Seed Oil Based Highly Branched Environment Friendly Polyester Resin/Clay Nanocomposites

To develop a high performance environment friendly material, highly branched polyester/clay nanocomposites have been prepared from Mesua ferrea Linn seed oil-based polyester resin and hydrophilic bentonite nanoclay. The prepared nanocomposites were characterized by Fourier transform infra-red spectroscopy, X-ray diffractometer, scanning electron microscope, transmission electron microscope and rheological studies. Partial exfoliation of clay layers by the polymer chains with good interfacial interactions was observed in the nanocomposites. The formation of delaminated nanocomposites was manifested through the enhancement of tensile strength, scratch hardness, chemical resistance, impact resistance, thermostability, etc. The results show enhancement of three times in tensile strength and 18 °C in thermostability by inclusion of 5 wt% nanoclay as compared to the pristine polymer. By the influence of 5 wt% nanoclay four times enhancement in elongation at break as compared to the pristine polymer was noticed. Thus these nanocomposites have the potential to be used in many advanced applications.     

防腐漆涂装含锌废水中锌粉的回收与利用

从水性环氧富锌涂料工业涂装废水中回收废锌粉,通过加热二甲基亚砜来溶解包覆于废锌粉表面的环氧树脂漆膜,得到回收锌粉,并将其再利用制防腐漆。在沉降时间12 h、热处理温度110 ℃、热处理时间60 min的条件下,废锌粉表面上的环氧树脂被去除,可直接以金属锌粉的形态加以回收利用,回收锌粉达到GB/T 6890—2012《锌粉》中的二级标准。使用后的溶剂经旋转蒸发后可再次使用,对锌粉的回收效果无影响。回收锌粉制备的防腐漆,其防腐蚀性能良好,可比市售锌粉。     

The separation of waste printed circuit board by dissolving bromine epoxy resin using organic solvent

Separation of waste printed circuit boards (WPCBs) has been a bottleneck in WPCBs resource processing. In this study, the separation of WPCBs was performed using dimethyl sulfoxide (DMSO) as a solvent. Various parameters, which included solid to liquid ratio, temperature, WPCB sizes, and time, were studied to understand the separation of WPCBs by dissolving bromine epoxy resin using DMSO. Experimental results showed that the concentration of dissolving the bromine epoxy resin increased with increasing various parameters. The optimum condition of complete separation of WPCBs was solid to liquid ratio of 1:7 and WPCB sizes of 16 mm² at 145 °C for 60 min. The used DMSO was vapored under the decompression, which obtained the regenerated DMSO and dissolved bromine epoxy resin. This clean and non-polluting technology offers a new way to separate valuable materials from WPCBs and prevent the environmental pollution of waste printed circuit boards effectively.     

Winery waste recycling through anaerobic co-digestion with waste activated sludge

In this study biogas and high quality digestate were recovered from winery waste (wine lees) through anaerobic co-digestion with waste activated sludge both in mesophilic and thermophilic conditions. The two conditions studied showed similar yields (0.40 m³/kgCOD_fed) but different biological process stability: in fact the mesophilic process was clearly more stable than the thermophilic one in terms of bioprocess parameters.The resulting digestates showed good characteristics for both the tested conditions: heavy metals, dioxins (PCDD/F), and dioxin like bi-phenyls (PCBs) were concentred in the effluent if compared with the influent because of the important reduction of the solid dry matter, but remained at levels acceptable for agricultural reuse. Pathogens in digestate decreased. Best reductions were observed in thermophilic condition, while at 37 °C the concentration of Escherichia coli was at concentrations level as high as 1000 UFC/g. Dewatering properties of digestates were evaluated by means of the capillary suction time (CST) and specific resistance to filtration (SRF) tests and it was found that a good dewatering level was achievable only when high doses of polymer (more than 25 g per kg dry solids) were added to sludge.     

Behavior of TiO2 nanoparticles during incineration of solid paint waste: A lab-scale test

In order to assess the potential impacts posed by products containing engineered nanoparticles, it is essential to generate more data about the release of these particles from products’ life cycle. Although first studies were performed to investigate the release of nanoparticles from use phase, very few data are available on the potential release from recycling or disposal of nano-enhanced products.In this work, we investigated the behavior of TiO₂ nanoparticles from incineration of solid paint waste containing these particles. Solid paint debris with and without TiO₂ nanoparticles were treated in a lab scale incineration plant at 950 °C (combustion temperature) and in oxidizing atmosphere. The obtained ashes were also vitrified with additives and the release of Ti was finally evaluated by leaching test. From our incineration lab-scale experiment, we did not observe a release of TiO₂ nanoparticles into the atmosphere, and Ti was attached to the surface of obtained solid residues (i.e. ashes). The characterization of ashes showed that TiO₂ nanoparticles reacted during the incineration to give calcium titanate. Finally, a very low release of Ti was measured, less 1 mg/kg, during the leaching test of ashes vitrified with glass cullet and feldspathic inert. Our work suggests that TiO₂ nanoparticles added in paints may undergo to physicochemical transformation during the incineration, and that Ti found in ashes may be strongly immobilized in glass matrix. Since this conclusion is based on lab-scale experiment, further research is required to identify which nanoparticles will be emitted to the environment from a real-word-incineration system of household hazardous waste.     

Composting kinetics in full-scale mechanical–biological treatment plants

This study focuses on the investigation of the kinetics of municipal solid waste composting in three full-scale mechanical–biological treatment (MBT) plants. The aims were to test a kinetic model based on volatile solids (VS) content change for describing the composting process in MBT plants, and to identify the model parameters that affected the estimation of the reaction rate constant most. To achieve this, VS content and several environmental conditions, namely temperature, moisture content, oxygen concentration and total bulk density were monitored throughout the composting process. Experimental data was fitted with a first-order kinetic model, and a rate constant (k) characteristic of composting under optimum environmental conditions was obtained. The kinetic model satisfactorily described the experimental data for the three MBT plants. k values ranged from 0.043 ± 0.002 d^?1 to 0.082 ± 0.011 d^?1. Sensitivity analysis showed that the model parameters that most affected the estimation of k were the initial biodegradable volatile solids content, the maximum temperature for biodegradation and the optimum moisture content. In conclusion, we show for the first time that full-scale MBT plants can be successfully modelled with a composting kinetic model.