The high strain-rate behaviour of three molecular weights of polyethylene examined with a magnesium alloy split-Hopkinson pressure bar

A traditional split-Hopkinson pressure bar system has been modified by the addition of ZK60A magnesium alloy pressure bars in order to increase the resolution of data when examining specimens of low-density, high-density and ultra-high molecular weight polyethylene. It was found that the low density of the ZK60A allowed a decent increase in transmitted pulse amplitude, whilst its relatively high yield strength afforded long-term reliability of the system. The accuracy of data obtained from the fitted strain gauges was verified with the use of a high-speed video camera, and was found to be an excellent match.     

High rate test method for fiber-matrix interface characterization

A new test method to directly characterize fiber-matrix interface properties under high rate of loading has been developed. A tensile Hopkinson bar with a modified incident bar is used to load a microdroplet test specimen. Numerical simulations were carried out to design the test specimen geometry and validate data reduction procedures for the dynamic interface experiments. Stress wave propagation in an S-2 Glass/Epoxy microdroplet specimen was studied with different droplet sizes (100 μm–200 μm) and fiber gage lengths (2 mm–6 mm). Simulation results indicate that dynamic equilibrium can be maintained up to a displacement rate of 10 m/s. Dynamic microdroplet experiments were conducted at a displacement rate of 1 m/s on S-2 glass/epoxy interface. Experimental results and post-failure inspection of the fiber matrix interface showed that the new test method is effective in measuring high rate interface properties of composites.     

High strain rate compression testing of intra-ply and inter-ply hybrid thermoplastic composites reinforced with Kevlar/basalt fibers

In this study, the influence of hybridization on the compression response of thermoplastic matrix-based composites under high strain rate loading was investigated. The intra-ply and inter-ply hybrid composites were manufactured with Kevlar/Basalt yarns as the reinforcements with Polypropylene as a matrix. Cylindrical composite specimens were laser cut from the flat compression moulded laminates. The composite specimens were loaded under high strain rate using split-Hopkinson pressure bar setup at strain rates ranging from 2815/s to 5481/s. The study revealed differences in the rate-dependent growth of peak stress, peak strain and toughness with the strain rate. Intra-ply hybrid composites with alternate weaving of Kevlar and basalt yarns exhibited highest peak stress as compared to the Inter-ply hybrid composites (alternate layers of Kevlar and basalt fabrics) and another intra-ply composite containing Kevlar in the warp and basalt in the weft direction. Whereas in inter-ply hybrid composite, with Kevlar as the loading face attained higher stress, while composite with Basalt as the loading face attained higher strain. SEM micrographs revealed that Kevlar on the loading face can bear the impact with lesser delamination as compared to the Basalt on the loading face. Damage studies revealed that Kevlar fiber surface loading results in higher stress as compared to basalt (brittle) surface loading with lower overall damage.     

High strain rate in-plane shear behavior of composites

Studies are presented on in-plane shear properties of a typical plain weave E-glass/epoxy composite under high strain rate loading. In-plane shear properties were determined with ±45 degree off-axis compression and tension tests using a split Hopkinson pressure bar apparatus. In-plane shear properties are presented as a function of axial and shear strain rates. The range of axial strain rates for off-axis compression tests was 819–2003 per sec, and for off-axis tension tests was 91–180 per sec, whereas the range of shear strain rates for off-axis compression tests was 1388–3442 per sec and for off-axis tension tests was 153–303 per sec. In general, it was observed that in-plane shear strength was enhanced at high strain rate loading compared to that at quasi-static loading. Also, it was observed that in-plane shear strength increased with increasing strain rate within the range of strain rates considered.     

Development of selective and chemically stable coating for stir bar sorptive extraction by molecularly imprinted technique

A novel stir bar coated with molecularly imprinted polymer (MIP) as selective extraction phase for sorptive extraction of triazine herbicides was developed. The stir bar was prepared by chemically bonding the MIP to the glass bar to improve its stability. A homogeneous and porous structure was observed on the stir bar surface. Extraction performance shows that the MIP-coated stir bar has stronger affinity to the template molecule terbuthylazine as compared with that of the reference stir bar without addition of template. Owning to the shape and structural compatibility, the obtained stir bar also demonstrated specific selectivity to the structural related-compounds of nine triazines, and thus can be applied to simultaneous determination of these compounds from complex samples coupled with high performance liquid chromatography. Four complex samples with different matrix, including rice, apple, lettuce and soil were used to evaluate this proposed method. The limits of detection obtained are in the range of 0.04-0.12 μg L⁻¹, and the recoveries for the spiked rice, apple, lettuce and soil samples were 80.8-107.7%, 80.6-107.8%, 72.0-109.8% and 89.0-114.8% with RSD from 1.2 to 7.9%, respectively. Moreover, this MIP-coated stir bar was firm, durable and can be prepared simply and reproducibly. The developed coating method would be useful to prepare a range of selective stir bars in order to extend the applicability of stir bar sorptive extraction (SBSE) in complex sample analysis.     

Asymmetrical flow field-flow fractionation technique for separation and characterization of biopolymers and bioparticles

Field-flow fractionation (FFF) is one of the most versatile separation techniques in the field of analytical separation sciences, capable of separating macromolecules in the range 10³–10¹⁵ g mol⁻¹ and/or particles with 1 nm–100 μm in diameter. The most universal and most frequently used FFF technique, flow FFF, includes three types of techniques, namely symmetrical flow FFF, hollow fiber flow FFF, and asymmetrical flow FFF which is most established variant among them. This review provides a brief look at the theoretical background of analyte retention and separation efficiency in FFF, followed by a comprehensive overview of the current status of asymmetrical flow FFF with selected applications in the field of biopolymers and bioparticles.     

Development of new polar monolithic coatings for stir bar sorptive extraction

Polar vinyl monomers have been used for the synthesis of several polymer monoliths, to serve as novel coatings for stir bar sorptive extraction; the monovinyl monomers 2‐hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol) monomethacrylate) (PEGMA) were copolymerized with (apolar) divinylbenzene (DVB) and/or pentaerythritol triacrylate (PETRA), both of which are cross‐linking agents. After the optimization of the most important synthesis parameters, which included the ratio between total monomers and porogen, the nature of the porogen, and the monomer ratios, inter alia, three mechanically stable, polar monolithic coatings for stir bar sorptive extraction were obtained that were based on poly(HEMA‐co‐DVB), poly(HEMA‐co‐PETRA), and poly(PEGMA‐co‐PETRA). Thereafter, and in order to evaluate the hydrophilicity of the resulting monoliths, they were applied as materials in the stir bar sorptive extraction of a group of emerging pollutants with a wide range of polarities. The results showed that both the poly(HEMA‐co‐DVB) and poly(PEGMA‐co‐PETRA) materials could be used to extract both polar and nonpolar compounds by stir bar sorptive extraction, in an effective manner. Taking into account the desired chemical and morphological properties, as well as the extraction efficiencies, the poly(PEGMA‐co‐PETRA) material seemed to be a particularly promising monolith for application as a novel coating in stir bar sorptive extraction.     

Development of a stir bar sorptive extraction method for the determination of volatile compounds in orange juices

A stir bar sorptive extraction method for the determination of volatile compounds in orange juices was developed. The extraction variables were optimized using a reduced two‐level factorial screening design (2^5‐1), and the most suitable analytical conditions for the extraction of the studied compounds were: sample volume 10 mL, extraction time 60 min, stirring speed 1800 rpm, NaCl amount 30% (weight/volume), and twister length 10 mm. The optimized method was further validated, obtaining good linearity and detection and quantification limits low enough to correctly determine the studied compounds. As well, for most of the studied compounds precision and recovery values were good. Several orange juice samples (squeezed and commercial) were extracted following the optimized extraction method and analyzed by gas chromatography coupled to mass spectrometry detection. The method has proven to be suitable for the determination of the aroma of orange juice, of which limonene was the major volatile compound in all the studied samples.     

General capillary pressure and relative permeability expressions for through-plane fluid transport in thin fibrous sheets

The rate of fluid transport in partially saturated porous media depends on the media's instantaneous (function of saturation) relative permeability, k_r(S), and capillary pressure, P_c(S). Obtaining functional relationships for relative permeability and capillary pressure is only possible via experimentation or expensive microscale simulations, and needs to be repeated for different media having different fiber diameters, thicknesses, or porosities. In this concern, we conducted series of 3-D microscale simulations to investigate the effect of the above parameters on the relative permeability and capillary pressure of fibrous porous sheets. The results of our parameter study are utilized to develop general expressions for k_r(S) and P_c(S). Our general expressions are based on the existing empirical correlations of two-phase flow in granular media, and can easily be included in macroscale fluid transport equations to predict the rate of fluid release from partially saturated fibrous sheets in a time and cost-effective manner.     

Stir bar sorptive extraction for the analysis of wine cork taint

A magnetic stir bar with a polydimethylsiloxane coating was used to absorb 2,4,6-trichloroanisole, 2,3,4,5-tetrachloroanisole, pentachloroanisole and their respective phenols from synthetic and real wine samples. The stir bar sorptive extraction method was optimised to obtain the best extraction conditions in terms of temperature, time, pH and NaCl addition. The stir bar was desorbed in a thermal desorption system coupled to a gas chromatograph-mass spectrometer. The method proposed showed good linearity over the concentration range tested and correlation coefficients ranged from 0.96 to 0.99 for all the analytes. The reproducibility and repeatability of the method was estimated between 1.29 and 4.02%. With no a pre-concentration step and with a much reduced analysis time, all the analyzed compounds showed detection and quantification limits that were lower than those observed with other methods found in the bibliography. Except for pentachlorophenol due to its poor absorptivity in polydimethysiloxane, in red wines, LOD ranged between 7.56 and 61.56 pg/l, and LOQ ranged between 17.21 and 205.11 pg/l; while in white wines, the LOD ranged between 5.82 and 30.50 pg/l and LOQ ranged between 19.41 and 101.61 pg/l. These concentrations were always lower than their respective olfactory thresholds values.     

Applications of capillary supercritical fluid chromatography to the characterization of edible oils and traditional chinese medicines

A home-made supercritical fluid chromatograph fitted with a capillary micropacked column and equipped with FID detection has been used to separate the components of silicone DC-200, beeswax, tea oil, cod-liver oil, rancid butter, and several traditional Chinese medicines such as Honghua oil, Jiuxin oil, and Wanhua oil.     

The use of thermogravimetric analysis technique for the characterization of construction materials

The thermogravimetric analysis (TG) technique is widely used in the characterization of diverse types of construction materials related to binders, such as plasters, limes and cements. For calcium sulphate dihydrate (gypsum) two serial dehydration steps are very near in temperature decomposition and overlapping in the thermogravimetric events is observed. The goal of this research is to develop new thermogravimetric analysis procedures that allow obtaining more precise information in the characterization of plasters. The resolution of both dehydration events has been increased using two different strategies: on one hand, the production in the experience of a water vapour self-generated atmosphere by the use of sealed aluminium pan with a pinholed lid. On the other hand, the use of high resolution thermogravimetric analysis (HRTG), based on the variation of the heating rate as a function of the rate of mass loss observed at once. The results obtained for both strategies of improvement of the TG curves, showed that they are two procedures that let to obtain a total resolution of the two dehydration steps for gypsum.     

Optimization of a novel method for the organic chemical characterization of atmospheric aerosols based on microwave-assisted extraction combined with stir bar sorptive extraction

A practical analytical methodology based on coupling microwave-assisted extraction-stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry (MAE-SBSE-TD-GC-MS) was developed and validated for the characterization of several SVOC in atmospheric particulate matter (PM).The high enrichment capacity of SBSE makes it a powerful tool for improving detection limits and MAE has been useful for overcoming the long extraction times and high volumes of extraction solvent used in traditional methodologies. Relative to Soxhlet extraction followed by GC-MS analysis (EPA Methods 3540 and 8270C), the MAE-SBSE-TD-GC-MS methodology resulted with approximately 10⁴ times better detection limits. Detection limits ranged from 0.3 to 8.3 pg m⁻³ for pp′-DDD and decachlorobyphenyl, respectively in PM2.5, 24 m³ air sample. The performance of the optimized methodology gave good precisions, with R.S.D. less than 30% for most of the standards, and linearity within the range tested of 0.1-15 μg L⁻¹. Analysis of real PM samples resulted in the identification of compounds in the ng L⁻¹ range.     

Development of a new stir bar sorptive extraction coating and its application for the determination of six pesticides in sugarcane juice

In this article, a novel polydimethylsiloxane/activated carbon (PDMS‐ACB) material is proposed as a new polymeric phase for stir bar sorptive extraction (SBSE). The PDMS‐ACB stir bar, assembled using a simple Teflon^®/glass capillary mold, demonstrated remarkable stability and resistance to organic solvents for more than 150 extractions. The SBSE bar has a diameter of 2.36 mm and a length of 2.2 cm and is prepared to contain 92 μL of polymer coating. This new PDMS‐ACB bar was evaluated for its ability to determine the quantity of pesticides in sugarcane juice samples by performing liquid desorption (LD) in 200 μL of ethyl acetate and analyzing the solvent through gas chromatography coupled with mass spectrometry (GC‐MS). A fractional factorial design was used to evaluate the main parameters involved in the extraction procedure. Then, a central composite design with a star configuration was used to optimize the significant extraction parameters. The method used demonstrated a limit of quantification (LOQ) of 0.5–40 μg/L, depending on the analyte detected; the amount of recovery varied from 0.18 to 49.50%, and the intraday precision ranged from 0.072 to 8.40%. The method was used in the analysis of real sugarcane juice samples commercially available in local markets.     

Development of a new stir bar sorptive extraction method for the determination of medium‐level volatile thiols in wine

A fast, simple, and reliable analytical method for the determination of medium‐level volatile thiols in wines is presented. Stir bar sorptive extraction using ethylene glycol‐silicone coated stir bars has been used in combination with thermal desorption gas chromatography with mass spectrometry for the analysis of 4‐mercapto‐4‐methylpentan‐2‐one, 2‐furanmethanethiol, 3‐mercaptohexyl acetate, and 3‐mercaptohexanol in wine. Optimization of the extraction technique was performed using a two‐level fractional factorial design. For the extraction step, the optimum conditions were: Ethylene glycol and silicone coated stir bars, pH at 3.5, sample volume of 25 mL, extraction time of 90 min, NaCl content 4.0 g, and stirring speed at 500 rpm. The optimized method achieved good linearity for all studied compounds (r² > 0.995) and it provided detection limits of 21.52, 0.36, 0.73, and 2.55 μg/L for 4‐mercapto‐4‐methylpentan‐2‐one, 2‐furanmethanethiol, 3‐mercaptohexyl acetate, and 3‐mercaptohexanol, respectively. It was repeatable, with precisions lower than 18% relative standard deviation for both intraday and interday repeatability. The developed procedure is suitable for the determination of these kinds of compounds when they are present at medium concentration levels. It was finally applied to real wine samples with negative aroma derived from the high concentration levels of these compounds.     

pH-resistant titania hybrid organic-inorganic coating for stir bar sorptive extraction of drugs of abuse in urine samples followed by high performance liquid chromatography-ultraviolet visible detection

An organic-inorganic hybrid titania-hydroxy-terminated silicone oil (titania-OH-TSO) stir bar coating was prepared by sol-gel method. The extraction performance of titania-OH-TSO coated stir bar was evaluated and compared with poly(dimethysiloxane) (PDMS), poly(dimethysiloxane)-divinylbenzene (PDMS-DVB), poly(dimethysiloxane)-β-cyclodextrin (PDMS-β-CD) and C(18) coated stir bar with five polar drugs of abuse including amphetamine (PA), methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and ketamine (Ke) as the model analytes. The experimental results revealed that the titania-OH-TSO coated stir bar exhibited highly pH-resistant ability, good preparation reproducibility, superior selectivity and high extraction efficiency for the target compounds. Based on this fact, a new method of titania-OH-TSO coated stir bar sorptive extraction (SBSE) combined with high performance liquid chromatography (HPLC)-ultraviolet visible (UV) detection was developed for the analysis of five drugs of abuse in urine samples. The factors affecting the extraction efficiency of SBSE such as sample pH, desorption solvent, sample volume, extraction time, desorption time, stirring rate and ionic strength were investigated and the optimal extraction conditions were established. Under the optimized conditions, the limits of detection (LODs) for titania-OH-TSO coated SBSE-HPLC-UV determination of five polar drugs of abuse were in the range of 2.3-9.1 μg/L with relative standard deviations (RSDs) ranging from 7.3 to 8.9% (c=300 μg/L, n=6), and all of the target compounds exhibited good linearity over a concentration range of 30-3000 μg/L. The developed method was applied to the determination of amphetamines and Ke in urine samples of drug abusers with satisfactory results.     

Density measurements under pressure for the binary system (ethanol + methylcyclohexane)

The density of the asymmetrical binary system composed of ethanol and methylcyclohexane has been measured under pressure using a vibrating tube densimeter. The measurements have been performed for eight different compositions as well as the pure compounds at eight temperatures in the range 283.15 K to 353.15 K and ten isobars up to 45 MPa. The uncertainty for the reported densities is estimated to be 0.1 kg · m⁻³. A non-monotonical behavior involving a minimum in the density versus composition has been found for this binary system. The measured data have been used to study the behavior and influence of temperature, pressure and composition on the excess molar volume, the isothermal compressibility, and the isobaric thermal expansion, revealing that a volume expansion occurs for this binary system. The results have been interpreted as due to changes in the intermolecular distances or free-volume, disruption of the order molecular structure and the breaking of hydrogen bonds within the self-associating alcohol.