Vitrification during the isothermal cure of thermosets

The process of vitrification that occurs during the isothermal cure of a cross-linking system at temperatures below T _g∞, the glass transition temperature of the fully cured resin, has been studied by TOPEM, a new temperature modulated DSC (TMDSC) technique based upon the use of stochastic temperature pulses. A comparison is made between TOPEM and another TMDSC technique, and some advantages of TOPEM are considered. The TOPEM technique is used to show that the mobility factor is not always a reliable approach to predicting the cure rate during vitrification, in view of its frequency dependence. Also, the dependence of the apparent vitrification time on frequency is examined. There appears to be a non-linear relationship between the apparent vitrification time and log(frequency), which is further discussed in the second part of this series.     

Identification of inorganic ions in post‐blast explosive residues using portable CE instrumentation and capacitively coupled contactless conductivity detection

Novel CE methods have been developed on portable instrumentation adapted to accommodate a capacitively coupled contactless conductivity detector for the separation and sensitive detection of inorganic anions and cations in post‐blast explosive residues from homemade inorganic explosive devices. The methods presented combine sensitivity and speed of analysis for the wide range of inorganic ions used in this study. Separate methods were employed for the separation of anions and cations. The anion separation method utilised a low conductivity 70 mM Tris/70 mM CHES aqueous electrolyte (pH 8.6) with a 90 cm capillary coated with hexadimethrine bromide to reverse the EOF. Fifteen anions could be baseline separated in 7 min with detection limits in the range 27–240 μg/L. A selection of ten anions deemed most important in this application could be separated in 45 s on a shorter capillary (30.6 cm) using the same electrolyte. The cation separation method was performed on a 73 cm length of fused‐silica capillary using an electrolyte system composed of 10 mM histidine and 50 mM acetic acid, at pH 4.2. The addition of the complexants, 1 mM hydroxyisobutyric acid and 0.7 mM 18‐crown‐6 ether, enhanced selectivity and allowed the separation of eleven inorganic cations in under 7 min with detection limits in the range 31–240 μg/L. The developed methods were successfully field tested on post‐blast residues obtained from the controlled detonation of homemade explosive devices. Results were verified using ion chromatographic analyses of the same samples.     

Selective extraction and elution of weak bases by in-line solid-phase extraction capillary electrophoresis using a pH step gradient and a weak cation-exchange monolith

A polymer monolith bearing weak cation-exchange functionality was prepared for the purpose of demonstrating pH-selective extraction and elution in in-line solid-phase extraction-capillary electrophoresis (SPE-CE) utilising a model set of cationic analytes, namely imidazole, lutidine and 3-phenylpropanamine. Optimization of the electrolyte conditions for efficient elution of the adsorbed analytes using a moving pH boundary required that the capillary and monolith be filled with 44 mM sodium acetate at high pH (pH 6) and a low pH electrolyte of 3 mM sodium acetate pH 3 was placed in the electrolyte vials. This combination allowed the adsorbed analytes to be simultaneously eluted and focused into narrow bands, with peak widths of the eluted analytes having a baseline width of 1.2 s immediately after the monolith. Using these optimum elution conditions, the versatility of the SPE-CE approach was demonstrated by removing unwanted adsorbed components after extraction with a wash at a different pH and also by selecting a pH at which only some of the model weak bases were ionised. The analytical performance of the approach was evaluated and the relative standard deviation for peak heights, peak area and migration times were in the ranges of 1.4-5.3, 1.2-3.3 and 0.4-1.2% respectively. Analytes exhibited linear calibrations with r(2) values ranging from 0.996 to 0.999 over two orders of magnitude. Analyte pre-concentration provided excellent sensitivity, and limits of detection for the analyte used in this study were in the range 8.0-30 ng ml(-1), which was an enhancement of 63 when compared to normal hydrodynamic injection occupying 1.3% of the capillary of these bases in water.     

Automation of solid-phase microextraction on a 96-well plate format

Studies have been performed assessing the feasibility and characterizing the automation of solid-phase microextraction (SPME) on a multi-well plate format. Four polycyclic aromatic hydrocarbons (PAHs), naphthalene, fluorene, anthracene and fluoranthene, were chosen as test analytes to demonstrate the technique due to their favorable partition coefficients, K(fw), between polydimethylsiloxane (PDMS) extraction phases and water. Four different PDMS configurations were investigated regarding their suitability. These included (i) a PDMS membrane; (ii) a multi-fiber device containing lengths of PDMS-coated flexible wire; (iii) a stainless steel pin covered with silicone hollow fiber membrane and (iv) commercial PDMS-coated flexible metal fiber assemblies. Of these configurations, the stainless steel pin covered with silicone tubing was chosen as a robust alternative. An array of 96 SPME devices that can be placed simultaneously into a 96-well plate was constructed to demonstrate the high-throughput potential when performing multiple microextractions in parallel. Different agitation methods were assessed including magnetic stirring, sonication, and orbital shaking at different speeds. Orbital shaking whilst holding the SPME device in a stationary position provided the optimum agitation conditions for liquid SPME. Once the analytes had been extracted, desorption of the analytes into an appropriate solvent was investigated. Liquid-phase SPME and solvent desorption on the multi-well plate format is shown to be a viable alternative for automated high-throughput SPME analysis compatible with both gas- and liquid-chromatography platforms.     

Extending colorings of locally planar graphs

Suppose G is a graph embedded in S_g with width (also known as edge width) at least 264(2^g−1). If P ⊆ V(G) is such that the distance between any two vertices in P is at least 16, then any 5‐coloring of P extends to a 5‐coloring of all of G. We present similar extension theorems for 6‐ and 7‐chromatic toroidal graphs, for 3‐colorable large‐width graphs embedded on S_g with every face even‐sided, and for 4‐colorable large‐width Eulerian triangulations. © 2001 John Wiley & Sons, Inc. J Graph Theory 36: 105–116, 2001     

Silica nanoparticle-templated methacrylic acid monoliths for in-line solid-phase extraction–capillary electrophoresis of basic analytes

Polymeric ion-exchange monoliths typically exhibit low capacities due to the limited surface area on the globules of the monoliths. The ion-exchange binding of protonated weakly basic analytes on deprotonated carboxylate sites on methacrylate polymer monoliths has been increased by templating the monoliths with silica nanoparticles. The templating method is achieved by adding the nanoparticles as a suspension to the polymerisation mixture. After polymerisation, the nanoparticles are removed by washing the monolith with strong base. Monolithic columns prepared using this procedure have exhibited a 33-fold increase in ion-exchange capacity when compared to untemplated monoliths prepared and treated under similar conditions. The templating procedure does not alter the macroporous properties of the polymer monolith, confirmed through scanning electron microscopy and BET surface area analysis, but provides increased capacity predominantly through the re-orientation of more carboxylic acid groups. The resulting increase in ion-exchange capacity has proven to be useful for the preconcentration and separation of neurotransmitters by in-line solid-phase extraction–capillary electrophoresis. The increased capacity of the templated monolith allowed the injection time to be increased 10 times over that of an untemplated monolith, allowing 10 times more sample to be injected with the efficiencies and recoveries remaining unaffected. The enhancement in sensitivity for the test mixture of neurotransmitter (dopamine, norepinephrine and metanephrine) ranged 1500–1900 compared to a normal hydrodynamic injection in capillary electrophoresis. Efficiencies obtained for the neurotransmitters were 100 000–260 000 plates, typical of those obtained in capillary zone electrophoresis. The applicability of the increased capacity silica nano-templated polymer monolith was demonstrated by analysing trace levels of caffeine in biological, food and environmental samples.     

High Temperature Semibatch Free Radical Copolymerization of Dodecyl Methacrylate and Styrene

Summary: High temperature semibatch free radical copolymerizations of dodecyl methacrylate (DMA) and styrene (ST) were carried out. A mechanistic model including depropagation and penultimate chain growth was built in Predici®. The comparison between the simulated and the experimental final polymer molecular weights indicates that the initiator efficiency decreases when DMA is used as a comonomer. Using estimated initiator efficiencies and termination coefficients, the model provides good fits to the complete set of experimental data.     

Tension–torsion fracture experiments – Part II: Simulations with the extended Gurson model and a ductile fracture criterion based on plastic strain

An extension of the Gurson model that incorporates damage development in shear is used to simulate the tension–torsion test fracture data presented in Faleskog and Barsoum (2013) (Part I) for two steels, Weldox 420 and 960. Two parameters characterize damage in the constitutive model: the effective void volume fraction and a shear damage coefficient. For each of the steels, the initial effective void volume fraction is calibrated against data for fracture of notched round tensile bars and the shear damage coefficient is calibrated against fracture in shear. The calibrated constitutive model reproduces the full range of data in the tension–torsion tests thereby providing a convincing demonstration of the effectiveness of the extended Gurson model. The model reinforces the experiments by highlighting that for ductile alloys the effective plastic strain at fracture cannot be based solely on stress triaxiality. For nominally isotropic alloys, a ductile fracture criterion is proposed for engineering purposes that depends on stress triaxiality and a second stress invariant that discriminates between axisymmetric stressing and shear dominated stressing.     

Mode III effects on interface delamination

For crack growth along an interface between dissimilar materials the effect of combined modes I, II and III at the crack-tip is investigated. First, in order to highlight situations where crack growth is affected by a mode III contribution, examples of material configurations are discussed where mode III has an effect. Subsequently, the focus is on crack growth along an interface between an elastic-plastic solid and an elastic substrate. The analyses are carried out for conditions of small-scale yielding, with the fracture process at the interface represented by a cohesive zone model. Due to the mismatch of elastic properties across the interface the corresponding elastic solution has an oscillating stress singularity, and this solution is applied as boundary conditions on the outer edge of the region analyzed. For several combinations of modes I, II and III crack growth resistance curves are calculated numerically in order to determine the steady-state fracture toughness. For given values of K_I and K_II the minimum fracture toughness corresponds to K_III=0 in most of the range analyzed, but there is a range where the minimum occurs for a nonzero value of K_III.