A method to determine volatile contaminants in polyethylene terephthalate (PET) packages by HDC-GC-FID and its application to post-consumer materials

A simple and low cost method to determine volatile contaminants in post-consumer recycled PET flakes was developed and validated by Headspace Dynamic Concentration and Gas Chromatography-Flame Ionization Detection (HDC-GC-FID). The analytical parameters evaluated by using surrogates include: correlation coefficient, detection limit, quantification limit, accuracy, intra-assay precision, and inter-assay precision. In order to compare the efficiency of the proposed method to recognized automated techniques, post-consumer PET packaging samples collected in Brazil were used. GC-MS was used to confirm the identity of the substances identified in the PET packaging. Some of the identified contaminants were estimated in the post-consumer material at concentrations higher than 220 ng.g-1. The findings in this work corroborate data available in the scientific literature pointing out the suitability of the proposed analytical method.

Drag reduction by polyethylene glycol in the tail arterial bed of normotensive and hypertensive rats

This study was designed to evaluate the effect of drag reducer polymers (DRP) on arteries from normotensive (Wistar) and spontaneously hypertensive rats (SHR). Polyethylene glycol (PEG 4000 at 5000 ppm) was perfused in the tail arterial bed with (E+) and without endothelium (E-) from male, adult Wistar (N = 14) and SHR (N = 13) animals under basal conditions (constant flow at 2.5 mL/min). In these preparations, flow-pressure curves (1.5 to 10 mL/min) were constructed before and 1 h after PEG 4000 perfusion. Afterwards, the tail arterial bed was fixed and the internal diameters of the arteries were then measured by microscopy and drag reduction was assessed based on the values of wall shear stress (WSS) by computational simulation. In Wistar and SHR groups, perfusion of PEG 4000 significantly reduced pulsatile pressure (Wistar/E+: 17.5 ± 2.8; SHR/E+: 16.3 ± 2.7%), WSS (Wistar/E+: 36; SHR/E+: 40%) and the flow-pressure response. The E- reduced the effects of PEG 4000 on arteries from both groups, suggesting that endothelial damage decreased the effect of PEG 4000 as a DRP. Moreover, the effects of PEG 4000 were more pronounced in the tail arterial bed from SHR compared to Wistar rats. In conclusion, these data demonstrated for the first time that PEG 4000 was more effective in reducing the pressure-flow response as well as WSS in the tail arterial bed of hypertensive than of normotensive rats and these effects were amplified by, but not dependent on, endothelial integrity. Thus, these results show an additional mechanism of action of this polymer besides its mechanical effect through the release and/or bioavailability of endothelial factors.

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

An amperometric lactate biosensor with lactate oxidase immobilized into a Prussian Blue (PB) modified electrode was fabricated. The advantage of using cetyltrimethylammonium bromide (CTAB) in the electrodeposition step of PB films onto glassy carbon surfaces was confirmed taking into account both the stability and sensitivity of the measurements. The biosensor was used in the development of a FIA amperometric method for the determination of lactate. Under optimal operating conditions (pH = 6.9, E = -0.1 V), the linear response of the method was extended up to 0.28 µmol L-1 lactate with a limit of detection of 0.84 mmol L-1. The repeatability of the method for injections of a 0.28 mmol L-1 lactate solution was 2.2 % (n = 18). The usefulness of the method was demonstrated by determining lactate in beer samples and the results were in good agreement with those obtained by using a reference spectrophotometric enzyme method.

LOCAL HEAD LOSS OF NON-COAXIAL EMITTERS INSERTED IN POLYETHYLENE PIPE

The design of a lateral line for drip irrigation requires accurate evaluation of head losses in not only the pipe but in the emitters as well. A procedure was developed to determine localized head losses within the emitters by the formulation of a mathematical model that accounts for the obstruction caused by the insertion point. These localized losses can be significant when compared with tire total head losses within the system due to the large number of emitters typically installed along the lateral line. Air experiment was carried out by altering flow characteristics to create Reynolds numbers (R) from 7,480 to 32,597 to provide turbulent flow and a maximum velocity of 2.0 m s(-1). The geometry of the emitter was determined by an optical projector and sensor An equation was formulated to facilitate the localized head loss calculation using the geometric characteristics of the emitter (emitter length, obstruction ratio, and contraction coefficient). The mathematical model was tested using laboratory measurements on four emitters. The local head loss was accurately estimated for the Uniram (difference of +13.6%) and Drip Net (difference of +7.7%) emitters, while appreciable deviations were found for the Twin Plus (-21.8%) and Tiran (+50%) emitters. The head loss estimated by the model was sensitive to the variations in the obstruction area of the emitter However, the variations in the local head loss did not result in significant variations in the maximum length of the lateral lines. In general, for all the analyzed emitters, a 50% increase in the local head loss for the emitters resulted in less than an 8% reduction in the maximum lateral length.

Influence of film thickness on the crystallization of Ni-doped amorphous silicon samples

This work reports on the crystallization of amorphous silicon (a-Si) films doped with 1 at. % of nickel. The films, with thicknesses ranging from 10 to 3000 nm, were deposited using the cosputtering method onto crystalline quartz substrates. In order to investigate the crystallization mechanism in detail, a series of undoped a-Si films prepared under the same deposition conditions were also studied. After deposition, all a-Si films were submitted to isochronal thermal annealing treatments up to 1000 degrees C and analyzed by Raman scattering spectroscopy. Based on the present experimental results, it is possible to state that (a) when compared to the undoped a-Si films, those containing 1 at. % of Ni crystallize at temperatures similar to 100 degrees C lower, and that (b) the film thickness influences the temperature of crystallization that, in principle, tends to be lower in films thinner than 1000 nm. The possible reasons associated to these experimental observations are presented and discussed in view of some experimental and thermodynamic aspects involved in the formation of ordered Si-Si bonds and in the development of Ni-silicide phases. (c) 2008 American Institute of Physics.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Polymer matrix sensitizing effect on photoluminescence properties of Eu(3+)-beta-diketonate complex doped into poly-beta-hydroxybutyrate (PHB) in film form

In this work is reported the sensitization effect by polymer matrices on the photoluminescence properties of diaquatris(thenoyltrifluoroacetonate)europium(III), [Eu(tta)(3)(H(2)O)(2)], doped into poly-beta-hydroxybutyrate (PHB) with doping percentage at 1, 3, 5, 7 and 10% (mass) in film form. TGA results indicated that the Eu(3+) complex precursor was immobilized in the polymer matrix by the interaction between the Eu(3+) complex and the oxygen atoms of the PHB polymer when the rare earth complex was incorporated in the polymeric host. The thermal behaviour of these luminescent systems is similar to that of the undoped polymer, however, the T(onset) temperature of decomposition decreases with increase of the complex doping concentration. The emission spectra of the Eu(3+) complex doped PHB films recorded at 298 K exhibited the five characteristic bands arising from the (5)D(0) -> (7)F(J) intraconfigurational transitions (J = 0-4). The fact that the quantum efficiencies eta of the doped film increased significantly revealed that the polymer matrix acts as an efficient co-sensitizer for Eu(3+) luminescent centres and therefore enhances the quantum efficiency of the emitter (5)D(0) level. The luminescence intensity decreases, however, with increasing precursor concentration in the doped polymer to greater than 5% where a saturation effect is observed at this specific doping percentage, indicating that changes in the polymeric matrix improve the absorption property of the film, consequently quenching the luminescent effect.

High Solids Content, Soap-Free, Film-Forming Latexes Stabilized by Laponite Clay Platelets

High solids content film-forming poly[styrene-co-(n-butyl acrylate)] [poly(Sty-co-BuA)] latexes armored with Laponite clay platelets have been synthesized by soap-free emulsion copolymerization of styrene and n-butyl acrylate. The polymerizations were performed in batch in the presence of Laponite and a methyl ether acrylateterminated poly(ethylene glycol) macromonomer in order to promote polymer/clay association. The overall polymerization kinetics showed a pronounced effect of clay on nucleation and stabilization of the latex particles. Cryo-transmission electron microscopy observation confirmed the armored morphology and indicated that the majority of Laponite platelets were located at the particle surface. The resulting nanostructured films displayed enhanced mechanical properties.

Sensorless synchronization method for thin-film direct optical broadband monitoring system

Optical monitoring systems are necessary to manufacture multilayer thin-film optical filters with low tolerance on spectrum specification. Furthermore, to have better accuracy on the measurement of film thickness, direct monitoring is a must. Direct monitoring implies acquiring spectrum data from the optical component undergoing the film deposition itself, in real time. In making film depositions on surfaces of optical components, the high vacuum evaporator chamber is the most popular equipment. Inside the evaporator, at the top of the chamber, there is a metallic support with several holes where the optical components are assembled. This metallic support has rotary motion to promote film homogenization. To acquire a measurement of the spectrum of the film in deposition, it is necessary to pass a light beam through a glass witness undergoing the film deposition process, and collect a sample of the light beam using a spectrometer. As both the light beam and the light collector are stationary, a synchronization system is required to identify the moment at which the optical component passes through the light beam.

Film thickness measurement techniques applied to micro-scale two-phase flow systems

Recently semi-empirical models to estimate flow boiling heat transfer coefficient, saturated CHF and pressure drop in micro-scale channels have been proposed. Most of the models were developed based on elongated bubbles and annular flows in the view of the fact that these flow patterns are predominant in smaller channels. In these models, the liquid film thickness plays an important role and such a fact emphasizes that the accurate measurement of the liquid film thickness is a key point to validate them. On the other hand, several techniques have been successfully applied to measure liquid film thicknesses during condensation and evaporation under macro-scale conditions. However, although this subject has been targeted by several leading laboratories around the world, it seems that there is no conclusive result describing a successful technique capable of measuring dynamic liquid film thickness during evaporation inside micro-scale round channels. This work presents a comprehensive literature review of the methods used to measure liquid film thickness in macro- and micro-scale systems. The methods are described and the main difficulties related to their use in micro-scale systems are identified. Based on this discussion, the most promising methods to measure dynamic liquid film thickness in micro-scale channels are identified. (C) 2009 Elsevier Inc. All rights reserved.

Polymer toughening using residue of recycled windshields: PVB film as impact modifier

In this work, poly(vinyl butyral) (PVB) film originated from the mechanical separation of windshields was tested as all impact modifier of Polyamide-6 (PA-6). The changes undergone by PVB film during the recycling process and the blend manufacturing were evaluated by thermal analyses, infrared spectroscopy and loss oil ignition. Blends of PA-6/original PVB film and PA-6/recovered PVB film were obtained in concentrations ranging from 90/10 to 60/40. The mechanical properties of the blends were investigated and explained in light of the blends morphologies, which in turns were correlated to the changes undergone by the PVB film during the recycling process. The original film presented a plasticizer content of 33 wt.%, which decreased to as low as 20 wt.%, after the recycling and blend preparation processes. The PA-6/PVB film blends presented lower values of tensile strength and Young`s modulus than Polyamide-6, but all blends presented a dramatic increase in their toughness, with a special feature for the 40 wt.%(, blend, which resulted in a super toughened material (impact strength exceeding 500 J/m). Similar results were obtained with recovered PVB film and super tough blends were also obtained. The use of recovered PVB resulted in a smaller improvement of the impact strength due to the loss of plasticizer undergone during the recycling process. The morphological observations showed that if the interparticle distance is smaller than around 0.2 mu m (critical value), the notched Izod impact strength values increase considerably and the fracture surface of blends exhibit characteristics of tough failure. (C) 2007 Elsevier Ltd. All rights reserved.

Application of the essential work of fracture method in ranking the performance in service of high-density polyethylene resins employed in pressure pipes

High-density polyethylene resins have increasingly been used in the production of pipes for water- and gas-pressurized distribution systems and are expected to remain in service for several years, but they eventually fail prematurely by creep fracture. Usual standard methods used to rank resins in terms of their resistance to fracture are expensive and non-practical for quality control purposes, justifying the search for alternative methods. Essential work of fracture (EWF) method provides a relatively simple procedure to characterize the fracture behavior of ductile polymers, such as polyethylene resins. In the present work, six resins were analyzed using the EWF methodology. The results show that the plastic work dissipation factor, beta w(p), is the most reliable parameter to evaluate the performance. Attention must be given to specimen preparation that might result in excessive dispersion in the results, especially for the essential work of fracture w(e).

Emissions from the premixed combustion of gasified polyethylene

An investigation was conducted on pollutants emitted from steady-state, steady-flow gasification and combustion of polyethylene (PE) in a two-stage furnace. The polymer, in pulverized form, was first pyrolyzed at 1000 degrees C, and subsequently, its gaseous pyrolyzates were burned, upon mixing with air at high temperatures (900-1100 degrees C). The motivation for this indirect type of burning PE was to attain nominally premixed combustion of the pyrolyzate gases with air, thereby achieving lower pollutant emissions than those emanating from the direct burning of the solid PE polymer. This work assessed the effluents of the two-stage furnace and examined the effects of the combustion temperature, as well as the polymer feed rate and the associated fuel/air equivalence ratio (0.3 < phi < 1.4). It was found that, whereas the yield of pyrolysis gas decreased with an increasing polymer feed rate, its composition was nearly independent of the feed rate. CO2 emissions peaked at an equivalence ratio near unity, while the CO emissions increased with an increasing equivalence ratio. The total light volatile hydrocarbon and semivolatile polycyclic aromatic hydrocarbon (PAH) emissions of combustion increased with an increasing equivalence ratio. The generated particulates were mostly submicrometer in size. Overall, PAH and soot emissions from this indirect burning of PE were an order of magnitude lower than corresponding emissions from the direct burning of the solid polymer, obtained previously in this laboratory using identical sampling and analytical techniques. Because pyrolysis of this polymer requires a nominal heat input that amounts to only a diminutive fraction of the heat released during its combustion, implementation of this technique is deemed advantageous.

Effect of precracking method on K(Ic) results for medium-density polyethylene tested under cryogenic condition

The effect of different precracking methods on the results of linear elastic K(Ic) fracture toughness testing with medium-density polyethylene (MDPE) was investigated. Cryogenic conditions were imposed in order to obtain valid K(Ic) values from specimens of suitable size. Most conservative K(Ic) values were obtained by slow pressing a fresh razor blade at the notch root of the specimen. Due to the low deformation level imposed on the crack tip region, the slow pressing razor blade technique also produced less scatter in fracture toughness results. It has been shown that the slow stable crack growth preceding catastrophic brittle failure during K(Ic) tests in MOPE under cryogenic conditions should not be disregarded as it has relevant physical meaning and may affect the fracture toughness results. (C) 2010 Elsevier Ltd. All rights reserved.

Influence of Water Content, Time, and Temperature on the Rheological Behavior of Polyethylene Terephtalate

In this work, the main factors affecting the rheological behavior of polyethylene terephtalate (PET) in the linear viscoelastic regime (water content, time delay before test, duration of experiment, and temperature) were accessed. Small amplitude oscillatory shear tests were performed after different time delays ranging from 300 to 5000 s for samples with water contents ranging from 0.02 to 0.45 wt %. Time sweep tests were carried out for different durations to explain the changes undergone by PET before and during small amplitude oscillatory shear measurements. Immediately after the time sweep tests, the PET samples were removed from the rheometer, analyzed by differential scanning calorimetry and their molar mass was obtained by viscometry analysis. It was shown that for all the samples, the delay before test and residence time within the rheometer (i.e. duration of experiment) result in structural changes of the PET samples, such as increase or decrease of molar mass, broadening of molar mass distribution, and branching phenomena. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3525-3533, 2010