Analysing metals in bottle‐grade poly(ethylene terephthalate) by X‐ray fluorescence spectrometry

After a rigorous cleaning process, recycled food‐grade poly(ethylene terephthalate) (PET), can be mixed with virgin PET resin in different concentrations and used for packaging of soft drinks. Therefore, it is important to have an experimental method to distinguish the presence of recycled polymer in a batch and to check its “true quality.” One of the issues to be verified is the presence of inorganic contaminants due to the recycling process. X‐ray fluorescence technique is one alternative for this kind of analysis. The results obtained in this work show that bottle‐grade PET samples (PET‐btg) are made either via direct esterification or by a transesterification process. Samples that were subjected to thermo‐mechanical processings (superclean® processing, PET‐btg blends processed in our laboratory and soft drink PET packaging) present Fe Kα emission lines with higher intensities than those presented by virgin bottle‐grade PET. After applying principal component analysis, it can be concluded that Fe is an intrinsic contaminant after the recycling process, furnishing a way to indicate class separations of PET‐btg. A calibration and validation partial least squares model was constructed to predict the weight percent of post‐consumption bottle‐grade PET in commercial PET samples. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of chlorine dioxide gas on physical,thermal, mechanical,and barrier properties of polymeric packaging materials

The effects of gaseous chlorine dioxide (ClO₂) on properties and performance of 10 selected polymeric packaging materials, including polyethylene (PE), biaxially oriented poly(propylene), polystyrene, poly(vinyl chloride), poly(ethylene terephthalate) (PET), poly(lactic acid), nylon, and a multilayer structure of ethylene vinyl acetate (EVA)/ethylene vinyl alcohol (EVOH), were evaluated. Physical, mechanical, barrier, and color properties as well as infrared (IR) spectra were assessed before and after polymer samples were exposed to 3600 ppmV ClO₂ gas at 23°C for 24, 168, and 336 h. The IR spectra of the ClO₂‐treated samples revealed many changes in their chemical characteristics, such as the formation of polar groups in the polyolefin, changes in functional groups, main chain scission degradation, and possible chlorination of several materials. The ClO₂‐treated PE samples showed a decrease in tensile properties compared with the untreated (control) films. Decreases in moisture, oxygen, and/or carbon dioxide barrier properties were observed in the treated PE, PET, and multilayer EVA/EVOH/EVA samples. A significant increase (P < 0.05) in the barrier to O₂ was observed in the ClO₂‐treated nylon, possibly the result of molecular reordering, which was found through an increase in the crystallinity of the material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological aspects of microbial hyaluronic acid

The rheological properties of the hyaluronic acid (HA) produced by the cultivation of Streptococcus zooepidemicus ATCC 39920 in synthetic medium at constant pH of 7.0 were determined. Relevant characteristics of the biopolymer as its pureness related to proteins (0.44 mg of protein per gram of HA) and its average molar weight (4.0 × 10⁶ Da) were also determined. Experimental data in steady shear (flow curves) have been correlated with the Cross model, which described the apparent viscosity shear rate data well mainly at concentrations higher than 50 mg mL^?1.The concentration dependence of specific viscosity showed two linear regimes that intercept at critical overlap concentration (c*) equal to 4 mg mL^?1. The storage (G′) and loss (G″) moduli increasing along the HA concentration and estimates out of the studied range indicate that a crossover frequency decreased with the increasing concentration of HA. The high concentration dependence of G′ as well as the deviations of the Cox‐Merz rule for most of the HA concentrations indicate the hyperentangled properties for the HA chains, which could be visualized through atomic force microscopy images even at low concentrations as 0.01 mg mL^?1. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Performance of vanadium-oxygen redox fuel cell

A promising approach to improving the energy density of the all-vanadium redox flow battery while also saving on raw materials costs, is to eliminate the positive half-cell electrolyte and replace it with an air electrode to produce a hybrid vanadium–oxygen redox fuel cell (VOFC). This concept was initially proposed by Kaneko et al. in 1992 and first evaluated at the University of New South Wales by Menictas and Skyllas-Kazacos in 1997. In this project the performance of the VOFC over a range of temperatures and using different types of membranes and air electrode assemblies was evaluated. Despite early problems with the membrane electrode assemblies that saw separation of the membrane due to swelling and expansion during hydration, with improved fabrication techniques, this problem was minimized and it was possible to operate a 5-cell VOFC system for a total of over 100 h without any deterioration in its performance.     

Formulation and characterization of leather and rubber wastes composites

Residues from footwear roughing and carding operations represent 5–15% (w/w) of the solid wastes generated by shoe‐making companies. These wastes are mainly composed by chromium tanned leather and sole materials, and are mostly land filled. Sometimes leaching tests show these wastes as hazardous due to chromium in the leachate. This work aims at a more sustainable option for these wastes by recycling them in styrene butadiene rubber (SBR) and acrylonitrile butadiene rubber (NBR). Thus, they were charged with: (i) ≤1 mm leather waste fibers in the range of 10–25 parts per hundred parts of rubber (phr); and (ii) leather and soles industrial carding and roughing wastes in the range of 20–100 phr. The leather waste fibers‐rubber composites tear strength is increased till 25 phr and both tension and elongation at break decrease within the acceptable range till 12.5 phr for SBR and 15 phr for NBR. In the case of leather and sole carding and roughing wastes, composites tear strength increases till 100 phr, and tension and elongation decrease within the acceptable range till 20 phr. The composite materials at the end of their life cycle may be considered inert or non‐hazardous wastes. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Characterization of Hemoglobin Adducts of 1,3-Dinitrobenzene and 1,3,5-Trinitrobenzene

1,3-dinitrobenzene (DNB) and 1,3,5-trinitrobenzene (TNB) are used primarily in explosive compositions and munitions and have been detected as environmental contaminants of surface waters as well as ground waters near production waste disposal sites. Hemoglobin (Hb) adducts have recently been proposed as biological markers of exposure assessment for various environmental compounds, including nitroaromatics. In the present study, we have investigated the formation of DNB and TNB hemoglobin adducts in vivo and in vitro in the blood of shrew (Cryptotis parva). DNB and TNB hemoglobin adducts were detected by GC/MS after either basic (0.1N NaOH) or acid (2N HCl) hydrolysis followed by organic solvent extraction and derivatization of the corresponding amines. The levels of DNB-Hb adducts detected after basic hydrolysis (238.7 ± 50.2 pg/mg Hb) are higher than the corresponding levels detected after acid hydrolysis (52.5 ± 16.2 pg/mg Hb). For the TNB-Hb the levels after acid hydrolysis (132.2 ± 37.8 pg/mg Hb) are higher than the levels detected after basic hydrolysis (44.7 ± 15.3 pg/mg Hb.) These results demonstrate the effectiveness of the hemoglobin adduct model for monitoring exposure to nitroaromatics.     

Development and Analysis of Three Diesel Particulate-Related Standard Reference Materials for the Determination of Chemical,Physical, and Biological Characteristics

The National Institute of Standards and Technology (NIST) has recently issued three Standard Reference Materials (SRMs) related to diesel particulate matter: SRM 1650a, Diesel Particulate Matter; SRM 2975, Diesel Particulate Matter (Industrial Forklift); and SRM 1975, Diesel Particulate Extract. These three materials have certified and reference concentrations for selected polycyclic aromatic hydrocarbons (PAHs) including many alkyl-substituted compounds. SRM 1650a is the reissue of an existing material and SRMs 2975 and 1975 represent new materials. The characterization of the PAH content of these three diesel particulate-related SRMs is presented with a discussion of the approach for the certification of PAH concentrations. In addition, the physical and biological characterization of these materials is discussed. A review of customer reported uses of these SRMs in the chemical, physical, and biological sciences is also provided.     

Chlorinated Polycyclic Aromatic Hydrocarbons Associated with Drinking Water Disinfection: Synthesis,Formation under Aqueous Chlorination Conditions and Genotoxic Effects

Polycyclic aromatic hydrocarbons (PAHs) are among the most persistent and toxic organic micropollutants present in water and several of them are mutagenic and carcinogenic. Although it has been shown that chlorinated derivatives of PAHs (Cl-PAHs) may be formed during the water chlorination procedure, little is known about their potential genotoxic and carcinogenic effects. The objectives of the present work were to prepare and characterize the major chlorinated derivatives of benzo[a]pyrene (BaP) and fluoranthene (Fluo), to develop an analytical methodology for their quantification in water samples and to analyse their potential genotoxicity. Chlorinated standards were prepared by a newly developed two phase method (water/n-hexane) using sodium hypochlorite. 6-Chloro-benzo[a]pyrene was selectively obtained from BaP, while 1,3-dichloro-fluoranthene and 3-chloro-fluoranthene were obtained from Fluo. All products were isolated and characterized by nuclear magnetic resonance and mass spectrometry. The formation of BaP- and Fluo-chlorinated derivatives under aqueous chlorination conditions was observed using a SPE-HPLC-FLD methodology. In addition, the cytotoxic and genotoxic activities of the three chlorinated derivatives were analyzed in comparison to their parent compounds, in a human-derived hepatoma cell line using the neutral red uptake and comet assays, respectively. The results showed that, at the equimolar doses of 100 and 125 μM, 6-Cl-BaP was able to induce a significantly higher level of DNA damage than BaP, suggesting a more potent genotoxic effect. In contrast, neither Fluo nor its chlorinated derivatives were genotoxic in the same cell line. The identification of new and possibly hazardous water chlorination by-product from PAHs emphasizes the need to minimize total organic carbon content of raw water and the implementation of safer water disinfection methods.     

Hybrid MCM-41 grafted by a general microwave-assisted procedure: a characterization study

Hybrid materials obtained through a Microwave-assisted grafting of organic functional groups on mesoporous silica (MCM-41 type) have been characterized by X-ray powder diffraction, TG-DSC, N₂ adsorption, solid state ¹³C- and ²⁹Si-NMR, TEM and SEM. The studied grafting procedure is effective in the preparation of hybrid organosilicas under solvent-free conditions. Microwaves allows an ultra-fast and clean functionalization of the mesoporous materials and the method has been applied to produce a wide series of functional materials. The hybrid materials maintain the original mesoporous structure when the loading of linked organic groups does not exceed 10 %. In this cases, the slight pore volume reduction is linearly correlated to the organic amount in the product. If functional groups able to interact among them through hydrogen bond are used, hybrid materials exhibit high Organic/SiO₂ ratios and low pore volumes due to the formation of a network occluding the pores, where functional groups of free organosilane molecules interacts with the functional groups of molecules linked to the matrix. NMR data confirm that the network is composed by organosilane molecules linked or not to the framework. Acid washing is able to labilize hydrogen bond and open the network. In the case of bulky but chemically inert functionalising agents the network is not produced.