Bio-Based Non-Isocyanate Urethane Derived from Plant Oil

A new bio-based non-isocyanate urethane was obtained by the reaction of a cyclic carbonate synthesized from a modified linseed oil and an alkylated phenolic polyamine (Phenalkamine) from cashew nut shell liquid. The incorporation of functional cyclic carbonate groups to the triglyceride units of the oil was done by reacting epoxidized linseed oil with carbon dioxide in the presence of a catalyst. Structural changes and changes in molar mass during the carbonation reaction were characterized using infrared spectrometry (FTIR) and chromatography. The aminolysis reaction of the cyclic carbonate with phenalkamine was monitored using real-time FTIR at 80 and 100?°C, respectively. The decay of the carbonate groups and the appearance of the newly built C=O groups of the urethane linkages were measured in situ through real-time FTIR spectra in dependence on the reaction time. Oscillatory time sweep measurements were used to monitor the viscoelastic properties of the system at 80 and 100?°C. The time of gelation was determined from rheometric measurements. Changes of the apparent activation energy with respect to the conversion of the reaction were calculated from isothermal measurements using Vyazovkin??s free kinetic model.     

From Natural Oils to Epoxy Resins: A New Paradigm in Renewable Performance Materials

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We describe the synthesis and properties of 100?% oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C₆F₅)₃) in toluene, allowed for controlled cationic polymerization at a very low concentration. Epoxidized oils (derived from triolein, soybean, and linseed oil) had varying epoxy content, rendering resins of different cross-link density. The polymerization was carried out at room temperature followed by post-curing at elevated temperature to speed up conversion. Epoxy resins were amorphous transparent glasses below glass transitions and hard rubbers above. Despite their high cross-link density, these materials show relatively low T_g’s reflecting the aliphatic nature of fatty acids and the presence of plasticizing “dangling” chains. The structure of the triglyceride starting oils influenced the properties of the resulting materials: the more regular structure of triolein compared to the very heterogeneous structures of soybean and linseed oils seemed to have enhanced some properties of the polymer networks. These epoxy polymers are potentially useful as encapsulating and potting compounds for electronic applications.

     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

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.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Biobased Epoxy/Layered Silicate Nanocomposites: Thermophysical Properties and Fracture Behavior Evaluation

The biobased epoxy containing epoxidized linseed oil (ELO) and its clay nanocomposites were processed with an anhydride curing agent. The certain amount of diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO. The selection of the DGEBF, ELO, an anhydride curing agent, and organo-montmorillonite clay resulted in an excellent combination, to provide new biobased epoxy/clay nanocomposites showing high elastic modulus, high glass transition temperature, and high fracture toughness with larger amount of ELO. Izod impact strength was almost constant while changing the amount of ELO. This is a promising result for future applications in different engineering industries.     

Biodegradation Behavior of Some Vegetable Oil-Based Polymers

The potential biodegradability of several vegetable oil-based polymers was assessed by respirometry in soil for 60–100 days at temperatures of 30–58°C. Films of soybean oil and linseed oil which were oxidatively polymerized (Co catalyst) on a kraft paper support were 90%–100% mineralized to CO₂ after 70 days at 30°C. Mineralization of polymerized tung oil to CO₂ was much slower than soy or linseed oils. Mineralization of epoxy resins made from epoxidized soybean oil (ESO) and aliphatic dicarboxylic acids was rapid while mineralization of similar resins made with a triacid (citric) was slower. There was no significant degradation of polyamine/ESO resins after 100 days at 58°C. Mineralization of the available carbon in vegetable oil polyurethanes and cationically polymerized ESO was less than 7.5% after 70 days at 30°C and 25 days at 55°C compared to 100% for soybean oil. From these results, it appears that triglycerides highly cross-linked with non-degradable linkages are not biodegradable to a significant extent while triglycerides cross-linked with hydrolysable bonds such as esters remain biodegradable.     

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.     

Effect of Magnesium Oxide Loading on Adhesion Properties of ENR 25/NBR Blend Adhesives in the Presence of Petro Resin and Gum Rosin Tackifiers

The adhesion properties of magnesium oxide filled epoxidized natural rubber (ENR 25)/acrylonitrile-butadiene rubber (NBR) blend adhesives were studied using petro resin and gum rosin as tackifiers. Toluene was used as the solvent throughout the experiment. Five different loadings, i.e. 10, 20, 30, 40 and 50 phr magnesium oxide was used in the adhesive formulation. The SHEEN hand coater was used to coat the adhesive on polyethylene terephthalate at 30 and 120 µm coating thickness. The tack, peel strength and shear strength were determined by a Lloyd adhesion tester operating at 30 cm min^?1. Results shows that all the adhesion properties of the ENR 25/NBR adhesives show a maximum value at 10 phr filler loading. Loop tack and peel strength pass through a maximum, an observation which is associated to the optimum wettability of adhesive on the substrate. For the shear test, maximum shear strength occurs due to the optimum cohesive strength of the adhesive. Results also show that all petro resin based adhesives have higher adhesion properties than gum rosin based adhesive. In all cases, the adhesion properties of adhesives also increase with increasing coating thickness.     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Effect of Hybrid Tackifiers on Adhesion Properties of Epoxidized Natural Rubber-Based Pressure-Sensitive Adhesives

Viscosity, peel and shear strength of epoxidized natural rubber (ENR)-based pressure-sensitive adhesive was studied by using hybrid tackifiers consisting of a mixture of coumarone-indene resin and petro resin. The coumarone-indene resin concentration was fixed at 40 parts per hundred parts of rubber (phr). The concentration of petro resin, however, was varied from 20 to 80 phr. Toluene and polyethylene terephthalate (PET) film were used as the solvent and coating substrate respectively throughout the experiment. Viscosity of adhesive was determined by a HAAKE Rotary Viscometer whereas peel and shear strength was measured by a Lloyd Adhesion Tester. Results show that viscosity and shear strength decreases with increasing petro resin concentration. However, peel strength exhibits a maximum value at 40 phr petro resin, an observation which is attributed to maximum wettability and compatibility of adhesive on the substrate. ENR 25-based adhesive exhibits higher viscosity and peel strength but lower shear strength compared to the ENR 50 adhesive system.     

14C-Photosynthesis of Phytoplankton in an Oligotrophic Alpine Lake (Traunsee,Austria) and its Response to Turbidity Caused by Industrial Tailings

The influence of industrial tailings on the biological integrity of the phytoplankton was assessed from annual measurements of photosynthetic rates in the alpine lake Traunsee. The mean annual integral production of 21 mmol C m^-2 d^-1 corresponded to the oligotrophic nature of the lake. Effects of effluents were tested by comparing photosynthesis at a station close to the industrial outlet (EB) and at a reference site with a maximum depth of 190 m (VI). Between-site optical properties (vertical attenuation coefficient, euphotic depth) were statistically significant different. The euphotic zone at the impacted station was on average 2 m shallower than at the reference site, owing to turbidity emanating from the industrial plant. The adaptation to low light intensities by the algal community at this station was evident from a high maximum light utilisation coefficient (^* at low light saturation (E _K). Algae at the deep reference site were photosynthetically less efficient but adapted to high light intensities. Photosynthetic adaptation to different light climates in the euphotic zone without significant quantitative biomass alterations at the impacted site gave a clear signature of biological integrity of the phytoplankton in the oligotrophic Traunsee.     

Biodegradation of acrylic acid polymers and oligomers by mixed microbial communities in activated sludge

The biodegradability (mineralization to carbon dioxide) of acrylic acid oligomers and polymers was studied in activated sludge obtained from continuous-flow activated sludge (CAS) systems exposed to mixtures of low molecular weight (Mw < 8000) poly(acrylic acid)s and other watesoluble polymers [poly(ethylene glycol)s] in influent wastewater. Dilute preparations of activated sludge from the CAS units were tested for their ability to mineralize acrylic acid monomer and dimer, as well as a series of model acrylic acid oligomers and polymers (Mw 500, 700, 1000, 2000, and 4500), as sole carbon and energy sources. Complete mineralization of acrylic acid monomer and dimer was observed in low-biomass sludge preparations previously exposed to the polymer mixture, based on carbon dioxide production and residual dissolved organic carbon analyses. Extensive (though incomplete) degradation was also observed for the low molecular weight acrylic acid oligomers (Mw 500 and 700), but degradation dropped off sharply for the 1000, 2000, and 4500 Mw polymers. Radiochemical (¹⁴C) data also confirmed the low degradation potential of the 1000, 2000, and 4500 Mw materials. Degradation of two commercial poly(ethylene glycol)s at 1000 and 3400 Mw was complete and comparable to that of the acrylic acid monomer and dimer. Our results indicate that mixed populations of activated sludge microorganisms can extensively metabolize acrylic acid oligomers of seven units or less. Complete mineralization, however, could be confirmed only for the monomer and dimer material, and carbon mass balance data suggested that the true molecular weight cutoff for complete biodegradation was significantly less than the 500–700 Mw range tested.     

Enhanced hydrolysis and methane yield by applying microaeration pretreatment to the anaerobic co-digestion of brown water and food waste

Microaeration has been used conventionally for the desulphurization of biogas, and recently it was shown to be an alternative pretreatment to enhance hydrolysis of the anaerobic digestion (AD) process. Previous studies on microaeration pretreatment were limited to the study of substrates with complex organic matter, while little has been reported on its effect on substrates with higher biodegradability such as brown water and food waste. Due to the lack of consistent microaeration intensities, previous studies were not comparable and thus inconclusive in proving the effectiveness of microaeration to the overall AD process. In this study, the role of microaeration pretreatment in the anaerobic co-digestion of brown water and food waste was evaluated in batch-tests. After a 4-day pretreatment with 37.5 mL-O₂/L_R-d added to the liquid phase of the reactor, the methane production of substrates were monitored in anaerobic conditions over the next 40 days. The added oxygen was consumed fully by facultative microorganisms and a reducing environment for organic matter degradation was maintained. Other than higher COD solubilization, microaeration pretreatment led to greater VFA accumulation and the conversion of other short chain fatty acids to acetate. This could be due to enhanced activities of hydrolytic and acidogenic bacteria and the degradation of slowly biodegradable compounds under microaerobic conditions. This study also found that the nature of inoculum influenced the effects of microaeration as a 21% and 10% increase in methane yield was observed when pretreatment was applied to inoculated substrates, and substrates without inoculum, respectively.     

Inkjet Printing for Silicon Solar Cells

Inkjet printing of metal nanoparticles is an attractive method for front-side metallization of silicon solar cells. It is owing to noncontact, low-cost, low-waste, and simple process. In this work, we proposed the ink-jet printing and electroless technology to fabricate the seed layer and electrode layer, respectively. Furthermore, we used electroplating method to increase the electrode conductivity. In this way, the energy conversion efficiency up to 12.22% without AR coating can be obtained on 100?×?100 mm c-Si cell.     

波长与辐射强度对活性艳蓝KN -R光催化降解的影响

以TiO2为光催化剂,分别测定了365 nm和254 nm两种紫外光源波长及辐射强度对活性艳蓝KN-R模拟废水处理效果的影响.实验结果表明:在波长365 nm紫外光源照射2h后,活性艳蓝KN-R降解率达69.1％,活性艳蓝KN-R的降解可用二级反应速率方程拟合；在波长254nm紫外光源照射1h后,活性艳蓝KN-R降解率...     

Preparation of Liquid Epoxidized Natural Rubber by Oxidative Degradations Using Periodic Acid,Potassium Permanganate and UV-Irradiation

Epoxidized natural rubber (ENR) needs to be degraded into shorter chain lengths, to form liquid epoxidized natural rubber (LENR), for applications such as coating and adhesives. Since ENR contains both C=C and epoxide groups as reactive sites for degradation reactions, thus, LENR could be prepared by different methods through cleavages of C=C or epoxide groups, or a combination of both sites. Different mechanisms would produce different terminals on the LENR. This paper reports the oxidative degradation by (a) periodic acid, (b) potassium permanganate and (c) ultra violet (UV) irradiation. The degraded rubbers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) and Fourier transform infra-red spectroscopy (FTIR). Ester and ketone terminals were formed in all the three methods, but lactone and hydrofuranic structures were observed only in degradation by UV irradiation. NMR spectrum reveals that cyclization of ENR has occurred during degradation by periodic acid. At lower periodic acid concentration, degradation takes place only via C=C cleavage, but at higher concentration, the attack to the epoxide groups becomes more prominent. Potassium permanganate has attacked both the double bonds and epoxide groups. On the other hands, epoxide group was not affected during degradation by UV irradiation, which cleaved only the C=C bonds.     

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.     

Thermal and Mechanical Properties of Polyurethane Rigid Foam Based on Epoxidized Soybean Oil

A soypolyol based on epoxidized soybean oil (ESO) was prepared in the presence of HBF₄ and diethanolamine (DEA) was used as ring opener. A series of polyurethane rigid foam were prepared by mixing polyol with TDI using an isocyanate index of 1.1. The polyol used in this paper were a mixture of soypolyol and a commercial PL-5601 polyester polyol and the mass fraction of PL-5601 was in the range of 0–60%. The thermal properties of the resins were characterized by DSC and TG. The results showed that these rigid foams possess high thermal stability. There were two glass transition temperature of each foam and Tg₁ was increasing with the increasing of OH value. The compression strength of the foam was also recorded, and the effect of mass ratio of soypolyol and PL-5601 polyester polyol on the compression strength was discussed.     

Fluorescence Verses Radioactivity Labeling for Lab-Scale Investigation of the Fate of Water-Soluble Polymers in Wastewater Treatment Plants

Water-soluble synthetic polymers are extensively used in cosmetics, detergents and paints. Many end up in wastewater and, later on, in wastewater-treatment plants. In order to gain an insight into their fate in such plants, fluorescence and radioactivity labelings were compared using a lab-scale reactor designed to mimic industrial conditions. Two fermentation media were considered, namely a mixture of E402 and E204 micro-organisms and an activated sludge collected from a water-treatment plant located in the south of France. A sample of low molar mass commercial poly(acrylic acid) (PAA) was labeled by radioactivity with tritium and by coupling the 6-aminofluorescein fluorescent dye. Labeled PAA-containing sludges were allowed to ferment. To monitor the fate of the polymers, aliquots of the fermented mixtures were withdrawn at selected times and centrifuged. Liquid and solid phases were analyzed by scintigraphy or UV spectrometry, depending of the labeling techniques. Both techniques led to similar distributions, c.a. 75% in the supernatant and 25% in the solid phase. Distributions remained constant during the biological tests. There was no degradation of the commercial PAA after aqueous size exclusion chromatography (SEC), in agreement with literature. These features showed that fluorescence-labeling can be used instead of the complex and expensive radiolabeling. The validated fluorescence-based method was then applied to a linear poly(acrylic acid) synthesized by ATRP and labeled with 6-aminofluorescein. There was no significant difference between the commercial and the linear poly(acrylic acid)s. In contrast, a linear PAA with 5% of tert-butyl ester repeating units was predominantly found in the solid phase although adsorption or absorption by micro-organisms could not be demonstrated. The method based on fluorescence labeling should be applicable to other water soluble polymers provided that the dye remains attached to the polymer as it was the case for the studied poly(acrylic acid)s.