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.     

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.     

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.     

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 Thixotropic Coatings Using Dimerized Soybean Oil Fatty Acids: The Case of Polyamide of 1,2-Phenylene Diamine

Soybean oil (SBO) was dimerized and the crude dimer acid product reacted with 1,2-phenylene diamine at 210 ± 5 °C under inert atmosphere to obtain fatty polyamide (FPA). The FPA was used to modify a commercial alkyd resin by reacting a mixture of the alkyd resin with 5 wt% of FPA at 120 °C for 80 min under inert atmosphere. The FTIR spectrum of the FPA modified resin showed evidence of higher degree of H-bonding than was found for the unmodified alkyd. White gloss coatings of 15, 20, 25, and 30% solids were formulated from the modified and unmodified resins and examined for performance with respect to: leveling, sag resistance, drying time, pigment settling, skinning tendency and film hardness. Results showed that the unmodified alkyd coatings exhibited good leveling but poor sag resistance at all solid contents. In contrast, FPA modified alkyd coatings combined good leveling with high sag resistance indicating their thixotropic nature. A strong tendency to pigment settling was observed for unmodified alkyd coatings but was not observed in the FPA modified alkyd coatings. The modified alkyd coatings showed skinning while the unmodified alkyd coatings did not skin. A 30% solids coating formulation of the FPA modified resin showed shorter surface dry time but longer hard dry time than the unmodified alkyd resin coating.     

Photocrosslinking of an Acrylated Epoxidized Linseed Oil: Kinetics and its Application for Optimized Wood Coatings

Over the past few decades, the industry developed an increasing interest in using renewable, bio-based thermosetting polymers as matrix systems for composites and coating systems. In the present paper an acrylated epoxidized linseed oil (AELO) was synthesized from epoxidized linseed oil (ELO) through ring opening of the oxirane group using acrylic acid as the ring opening agent. The synthesized AELO was mixed with three different photoinitiators and cured under monochromatic conditions (???=?365?nm) at different light intensities and at different temperatures. The concentration of the initiators was aligned that all initiators absorb at 365?nm the same amount of light. The evolution of cure was monitored by using real-time infrared spectroscopy with a heated attenuated total reflection unit. The decrease of absorption in the measured spectra at 1,406?cm^?1 was used to calculate the conversion of acrylic double bonds with increasing time of UV light exposure to get information about the cure kinetics for each AELO mixture at different light intensities and different temperatures. Wood substrates were coated in a preliminary work with the AELO mixtures and after UV-curing some technological coating properties like gloss, scratch resistance, adhesion, and solvent resistance were tested. In combination with the information about the cure kinetics in the present work the coating properties were correlated with the cure evolution and the final degree of double bond conversion. The found correlation can be used in the future to find optimized coating conditions for the AELO mixtures on wood substrates.     

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.     

Cetyltrimethyl Ammonium Bromide Modified Kaolin as a Reinforcing Filler for Natural Rubber

Cure characteristics, Mooney viscosity and physico-mechanical properties of natural rubber (NR) containing CTAB modified kaolin have been studied. NR mix containing 6 phr (parts per hundred part rubber) of CTAB modified kaolin showed significant increases in cure rate and state of cure as compared to gum NR compound and a mix containing the same amount of unmodified kaolin. Lower Mooney viscosity of the NR mix containing CTAB modified kaolin suggested improved processability. Reinforcing effect of CTAB modified kaolin in NR was evident from higher chemical crosslink density index, tensile modulus, hardness, tensile strength and tear strength. Besides, the NR vulcanizate containing 6 phr of CTAB modified kaolin showed lower abrasion loss and heat build-up which could be beneficial for applications such as tire treads.     

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.     

Synthesis of poly(hydroxyalkanoate) from hydrolyzed linseed oil

Pseudomonas putida was grown on a mixture of long-chain fatty acids obtained by hydrolysis of linseed oil. A poly(3-hydroxyalkanoate) containing 51.2% of unsaturated monomers was obtained. A considerable percentage (13.6%) was constituted by C₁₄ and C₁₆ monomers containing three double-bonds in the side chains. The polymer showed a high tendency to crosslink when it was kept in presence of air. In the crosslinked polymer no polyunsaturated monomers could be detected.     

PHB/V in Extrusion Coating of Paper and Paperboard—Study of Functional Properties. Part II

Extrusion coating experiments were carried out in the pilot line at Tampere University of Technology (Institute of Paper Converting). Commercially produced 3-hydroxybutyrate/3-hydroxyvalerate copolymer, commercial Finnish paper, and paperboard qualities were utilized as substrates. Functional properties, such as heat-sealing and hot-tack properties, pinhole density, and water vapor transmission rate were determined. PHB/V coatings exhibited approximately four–six times higher water vapor transmission rates (WVTR) than the corresponding LDPE coatings. The incorporation of wax or tall oil rosin into PHB/V improved its water vapor barrier. Curling of PHB/V was reduced by the addition of wax or tall oil rosin into the base polymer. PHB/V provided good heat-sealing characteristics at rather high sealing temperatures. Pinhole density was substantially reduced by using higher molecular weight PHB/V and by incorporating plasticizer into PHB/V.     

Morphological and Thermal Characterization of Linseed-Oil Based Polymers from Cationic and Thermal Polymerization

Linseed oil-based polymers have been synthesized via cationic and thermal polymerization and characterized through various techniques, such as SEM, DMA, DSC and TGA. The morphology of the polymer samples after extraction reveals the smooth structure of the polymer matrix. With an increase in oil content, the morphology is observed to be more loosely bound. With an increase in linseed oil content in the samples, the room temperature storage modulus (E′) varies from 10.4 × 10⁷ to 1.8 × 10⁷ Pa. The glass transition temperatures measured through DMA of the cationic samples ranges from 70 to −6 °C and the crosslink densities range from 18.4 × 10³ to 3.4 × 10³ mol/m³. The glass transition temperatures of the thermal samples range from 106 to −4 °C and the crosslink densities range from 7.7 × 10³ to 2.4 × 10³ mol/m³. The TGA results show three stages of degradation of the polymer samples and it is also revealed that these polymers are stable up to 200 °C, showing negligible decomposition.     

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.

     

High Toughness and Fast Crystallization Poly(Lactic Acid)/Polyamide 11/SiO<Subscript>2</Subscript> Composites

A poly(lactic acid) (PLA)/polyamide 11 (PA11)/SiO₂ composite was mixed from PLA, PA11, and nanosilica particles through twin-screw extrusion. The PLA/PA11/SiO₂ composite was evaluated with tensile and Izod impact tests, light transmission and haze measurement, and isothermal and nonisothermal crystallization behavior determinations. The PLA/PA11/SiO₂ (97.0/3.0) composite had approximately 10.8% less ultimate tensile strength than neat PLA, but it had greater ductility and approximately ninefold greater elongation at break. A dimple morphology was observed on the fractural surface of the PLA/PA11/SiO₂ composite, indicating that the incorporation of PA11 and nanosilica particles increased the ductility of the PLA matrix. PLA with less than 3 wt% of PA11 and 0.5 phr of nanosilica particles had an Izod impact strength of 8.72 kJ/m². PA11 and nanosilica particles effectively toughened this PLA polymer; they accelerated both isothermal and nonisothermal crystallization rates and increased the crystallinities of the resulting composites under isothermal and nonisothermal crystallization processes.     

Toxicity Evaluation with the Microtox Test to Assess the Impact of In Situ Oiled Shoreline Treatment Options: Natural Attenuation and Sediment Relocation

Changes in the toxicity levels of beach sediment, nearshore water, and bottom sediment samples were monitored with the Microtox^® Test to evaluate the two in situ oil spill treatment options of natural attenuation (natural recovery--no treatment) and sediment relocation (surf washing). During a series of field trials, IF-30 fuel oil was intentionally sprayed onto the surface of three mixed sediment (pebble and sand) beaches on the island of Spitsbergen, Svalbard, Norway (78°56^′ N, 16°45^′ E). At a low wave-energy site (Site 1 with a 3-km wind fetch), where oil was stranded within the zone of normal wave action, residual oil concentrations and beach sediment toxicity levels were significantly reduced by both options in less than five days. At Site 3, a higher wave-energy site with a 40-km wind fetch, oil was intentionally stranded on the beach face in the upper intertidal/supratidal zones, above the level of normal wave activity. At this site under these experimental conditions, sediment relocation was effective in accelerating the removal of the oil from the sediments and reducing the Microtox^® Test toxicity response to background levels. In the untreated (natural attenuation) plot at this site, the fraction of residual oil remaining within the beach sediments after one year (70%) continued to generate a toxic response. Chemical and toxicological analyses of nearshore sediment and sediment-trap samples at both sites confirmed that oil and suspended mineral fines were effectively dispersed into the surrounding environment by the in situ treatments. In terms of secondary potential detrimental effects from the release of stranded oil from the beaches, the toxicity level (Microtox^® Test) of adjacent nearshore sediment samples did not exceed the Canadian regulatory limit for dredged spoils destined for ocean disposal.     

Aging of Toughened Polylactic Acid Nanocomposites: Water Absorption,Hygrothermal Degradation and Soil Burial Analysis

The environmental aging behaviour of montmorillonite (MMT) filled polylactic acid (PLA) nanocomposites (PLA/MMT) and linear low density polyethylene (LLDPE)-toughened PLA (PLA/LLDPE ratio = 90/10) nanocomposites (PLA/LLDPE/MMT) were investigated in this study. The nanocomposites were subjected to water absorption, hygrothermal degradation and soil burial analysis. Both PLA/MMT and PLA/LLDPE/MMT nanocomposites were immersed in distilled water at three different temperatures (room temperature, 60, and 90 °C) and the weight difference before and after immersion was calculated. The kinetics of water absorption for both nanocomposites followed the Fick’s second law of diffusion, where a linear relationship exists between the initial moisture absorption at any time t and t ^1/2 (the square root of time), followed by a horizontal plateau (saturation). The equilibrium moisture content (M _m ) and diffusion coefficient (D) of PLA nanocomposites increased with the addition of MMT (2 phr) and LLDPE. However, the D values of both nanocomposites decreased by increasing MMT (4 phr). The M _m for PLA/MMT and PLA/LLDPE/MMT nanocomposites increased by increasing immersion temperature (60 °C) and prolonged immersion resulted in hygrothermal degradation of both nanocomposites. The hygrothermal degradation studies showed that PLA degrades much faster at 90 °C as compared to 60 °C in both the nanocomposites. The addition of MMT and LLDPE improved the hygrothermal stability of PLA in both nanocomposites. Soil burial test revealed deterioration of impact strength in all samples while the rate of biodegradation was retarded in the presence of MMT and LLDPE.     

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.     

Fluxes and Loading of Heavy Metals, Benzo[a]pyrene and Oil Products in Vilnius City

The concentrations of heavy metals Pb, Cd, Cu, Zn and Hg, benzo[a]pyrene and oil products (C₁₅–C₂₈) in bulk (wet and dry) atmospheric deposition in Vilnius city in 2005–2006 were analysed. The highest flux to the ground surface of the city residential area, reaching 1,680 mg m^?2 year^?1, was determined for oil products, which in atmospheric bulk deposition was estimated to be mainly in the form of solid sediments. Among heavy metals, the highest flux was determined for Zn (113.5 mg m^?2 year^?1), while the lowest flux was determined for Hg (0.06 mg m^?2 year^?1). The flux of investigated pollutants ranges from a few times, or for some pollutants, up to one order of magnitude higher at the urban sampling site in comparison to residential or background sites. Some hundred tons of oil products, approximately 52 tons of zinc and a considerably lower amount of mercury, benzo[a]pyrene and cadmium deposit yearly to the ground and water surface of Vilnius city. Metallic constructions related to transport and buildings, automobile exhausts, spills of fuel and lubricants are suggested to be the factors which result in the accumulation of high amounts of heavy metals, oil products and other pollutants on the ground surface of the city.     

Removal of Oil from Water by Calcium Alginate Hydrogel Modified with Maleic Anhydride

Calcium alginate hydrogel was prepared and used as a biosorbent for the removal of oil from aqueous solutions. Calcium alginate hydrogel was further chemically modified by esterification with maleic anhydride. The changes in the physicochemical properties of maleic anhydride modified calcium alginate were investigated via multiple techniques (FTIR, SEM, BET and DSC/TGA). Adsorption batch experiments were carried out to compare the oil adsorption capacities of native and modified calcium alginates. Adsorption experiments were carried out as a function of solution pH, temperature and ionic strength to determine the optimal conditions for the adsorption of oil. Equilibrium and kinetic studies were conducted for the modified alginate. Results revealed that the maleic anhydride modification of calcium alginate improved its adsorption capacity towards oil. Higher adsorption capacities of modified alginate were attained at lower temperatures (20 °C), higher ionic strengths (1.0 M NaCl) and within the pH range of 5–9. The oil adsorption data obtained for modified alginate could be better described by the first order kinetic model (R²?=?0.981) and the BET equilibrium isotherm (R²?=?0.984). The maximum monolayer adsorption capacity predicted by the BET model for the modified calcium alginate was found to be 143.0 mg/g.