Development and evaluation of terminally epoxidized triglycerides for coatings applications

Epoxidized 10-undecenoic acid triglyceride, an experimental seed oil derivative that has a terminal epoxy group on each of the three acyl glyceride segments, has been found to have good reactivity with amine curatives and allows room temperature cures to be obtained. Coatings based on epoxidized 10-undercenoic acid triglyceride have also shown excellent UV stability. As an example, coatings samples placed in a QUVA chamber exhibit no loss in gloss after 3000 hr of a cycled exposure to high intensity UV lamps and moisture at temperatures of 50–60°C. In comparison, coatings based on standard liquid epoxy resins (LERs) and commercially available hydrogenated LERs lose gloss due to chalking/decomposition within 200–800 hr. Presented at the 81 st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

Influence of very long aging on the relaxation behavior of flame‐retardant printed circuit board epoxy composites under mechatronic conditions

Very long aging times, up to 15,100 h (629 days) at 110°C, were achieved on flame‐retardant printed circuit board laminates commonly used in automotive design. This composite was fabricated from glass fibers embedded in an epoxy resin. Aging was performed in an oven under an air atmosphere at a temperature lower than the glass‐transition temperature. Temperature‐modulated differential scanning calorimetric analysis was used to investigate the influence of such aging on the glass‐transition phenomena. A new amorphous phase appeared during aging. By extending the analysis to samples collected at different thicknesses, we demonstrated the existence of a time‐dependent gradient of the properties. A skin–core structure was evidenced, and this slowed down oxidation and allowed physical aging to occur in the bulk sample. An exponential law described the variations of the glass‐transition of the new external compound. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 786‐792, 2013     

Effect of Maleic‐Anhydride Grafting on the Physical and Mechanical Properties of Poly(L‐lactic acid)/Starch Blends

MA is grafted onto both PLLA and starch in an internal mixer in the presence of DCP in a one‐step reactive compatibilization process. The effect of maleation of MA on the physical and mechanical properties and morphology of the blends was assessed. The onset decomposition temperature of the PLLA/starch blends decreased as the starch content increases due to the lower thermal stability of starch and the low effect of the maleation reaction on the thermal stability of the blends. PLLA/starch blends without grafted MA showed higher crystallinity as the starch content increased. Reactive compatibilized blends with less than 20 wt% starch had higher storage modulus, indicating that the compatibility between the two phases was improved.

     

Extractant Assisted Synthesis of Polymer Stabilized Platinum and Palladium Metal Nanoparticles for Sensor Applications

Abstract

Extractant‐assisted synthesis of platinum and palladium polymer‐stabilized metal nanoparticles (PSMNP) was carried out for the first time. The synthesis included the following sequential steps: a) loading of extractant (tributyl‐phosphine oxide, TBPO) with the desired metal ion; b) preparation of a membrane “cocktail” by mixing a metal‐containing extractant, solution of the polymer (PVC or polysulfone) and plastisizer; c) membrane deposition and metal reduction inside the membrane (intermatrix synthesis of PSMNP) by using either a chemical or an electrochemical reduction technique. The electro conductivity of the resulting polymer‐metal nanocomposite membrane appeared by several orders of magnitude higher than that of the metal‐free polymer. The mass‐exchange properties of PSMNP‐containing membranes were shown to depend on both the type of the polymer and the membrane deposition technique.     

CHARACTERIZATION AND COMPARISON OF SPECIATED ATMOSPHERIC CARBONACEOUS PARTICULATES AND THEIR POLYCYCLIC AROMATIC HYDROCARBON CONTENTS IN THE CONTEXT OF THE PASO DEL NORTE AIRSHED ALONG THE U.S.-MEXICO BORDER

Carbonaceous particulate matter (PM) was collected by both thermal precipitation and glass fiber filters from specific combustion sources and examined by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). PM from various natural gas burner combustion regimes (NGPM), burning tires (TPM), a heavy duty diesel truck (DPM), wood burning (WPM), candle burning (CPM), along with commercial black carbon (BC) powder and multiwall carbon nanotube (MWCNT) aggregates material exhibited similarities in PM microstructure, and average primary spherule diameters. The spherule structures consisted of curved graphene fragments and intercalated polycyclic aromatic hydrocarbons (PAH). PAH concentrations were measured and compared for these PMs, including PAH diagnostic ratios. An analysis of PAH carcinogenicity either as a carcinogenicity index or a potency equivalency factor from literature data indicated that only the TPM PAH content would pose any significant long term, carcinogenicity threat.     

Relative Genotoxicities of PAH of Molecular Weight 252 AMU in Coal Tar-Contaminated Sediment

Bioassay-directed chemical fractionation methodology was used to calculate relative mutagenic potencies of polycyclic aromatic hydrocarbons (PAH) of molecular weight 252 amu in coal tarcontaminated sediment from Sydney Harbour, Nova Scotia. A normal phase HPLC technique was used to separate organic solvent extracts into fractions containing isomeric PAH of a single benzologue class. Bioassays with Salmonella typhimurium strain YG1025 with the addition of oxidative metabolism (S9) showed that approximately 50% of the mutagenic activity observed in the sediment extract was associated with PAH of molecular weight 252 amu. Further separation of the 252 PAH fraction using reversed phase HPLC yielded subfractions containing individual compounds; bioassay dose-response curves for these subfractions showed that benzo[a]pyrene was responsible for approximately 75% of the activity of the 252 PAH fraction.     

Synthesis and Theoretical Study of New Guanylated Cyclophosphazenes and Their Use in the CO2 Fixation into Styrene Carbonate

Three new guanylated cyclophosphazenes G1–G3 have been synthesized through the catalytic guanylation of three different bi, tetra and hexa (p-aminophenoxy)-cyclophosphazenes by using N,N’-diisopropylcarbodiimide as guanylating agent, ZnEt₂ as catalyst and dry tetrahydrofuran as solvent. The resulting products have been characterized by ¹H, ¹³C{¹H} and ³¹P{¹H} NMR spectroscopy. The hexaguanylated cyclophosphazenes exhibit a deep purple colour, unusual for this type of compounds. The electronic structure of these compounds was investigated by carrying out density functional calculations at PBE-D3(BJ)/TZP level of theory. The molecular structural analysis reveals that aromatic rings are stacked and time dependent density functional calculations show that a charge transfer electronic transition occurs between the aromatic rings which absorb light around 500–700 nm. Finally, the catalytic usefulness of guanylated cyclophosphazene compounds G1–G3 has been proven by the preparation of styrene carbonate from the reaction between styrene oxide and carbon dioxide.

     

Poly(L‐lactic acid) with added α‐tocopherol and resveratrol: optical,physical, thermal and mechanical properties

Poly(L ‐lactic acid) (PLLA) films containing various concentrations of two natural antioxidants, α‐tocopherol and resveratrol, were fabricated by a melt compounding and compression molding process. The influence of the antioxidants on the optical properties such as color and UV‐visible light transmission was analyzed. The thermal, mechanical, rheological and physical properties of PLLA films with added antioxidants were assessed. PLLA films with added α‐tocopherol and resveratrol showed a yellowish brown color and the lightness was influenced by the presence of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. PLLA films with added antioxidants were slightly more hydrophobic than neat PLLA. The combination effect of plasticizing and enhancement of the elastic modulus with differing concentrations of two antioxidants played a critical role in the mechanical and thermomechanical properties of PLLA films. The melt viscosity of the PLLA films with added antioxidants was substantially higher than that of neat PLLA. The higher melt viscosity and G′(ω) could be an indication of formation of entanglement between PLLA and the two antioxidants. Copyright © 2012 Society of Chemical Industry     

An organically modified zirconate film as a corrosion-resistant treatment for aluminum 2024-T3

Current coating systems for aircraft corrosion protection are based on a traditional chromate surface treatment, primer, and topcoat. The Air Force is seeking environmentally benign corrosion-resistant surface treatments for aluminum-skinned aircraft as a replacement for environmentally hazardous surface treatments involving chromates. Performance of replacement treatments must be able to satisfy the durability needed for dramatically extended lifetimes, be compatible with present and future environmental requirements, and be easily integrated into current primer/topcoat paint systems.

Organically modified zirconate sol–gel films were investigated as an environmentally compliant replacement for chromated surface treatments, which included functionalized components to tailor the chemistry at both the aluminum oxide substrate/surface treatment interface and the surface treatment/topcoat interface. Sol–gel films were applied to aluminum 2024-T3 alloy coupons, and the resulting film chemistry was investigated. FTIR was used to identify organic components in the film and X-ray photoelectron spectroscopy was used to investigate the interface chemistry. The result of the chemically modified sol–gel synthesis was a coating in which a concentration gradient was formed at the surface, which is discussed. The corrosion protection attributes of these films was also studied and the electrochemical evaluation of sol–gel films will be discussed, both as stand-alone coatings and as part of a full coating system.

Organically modified sol–gels exhibited significantly better protection in terms of barrier properties in comparison to a typical chromate-based processes. The resulting data from evaluations of sol–gel produced coatings show promise towards the goal of producing a robust chemical interaction/bonding of such corrosion-resistant coatings on the surface of aluminum-skinned aircraft without the use of environmentally hazardous chromate agents.