Separation of polyolefins based on comonomer content using high‐temperature gradient adsorption liquid chromatography with a graphitic carbon column

This report describes the application of a recently developed polyolefin characterization tool based upon gradient adsorption high‐temperature liquid chromatography (HT‐LC) using a graphitic carbon stationary phase to polyolefin homopolymer and previously unreported copolymer systems. Polyolefin‐based materials find utility in a broad range of applications and are differentiated by parameters such as molecular weight and comonomer content. Polymer comonomer distribution is commonly determined by crystallinity‐based separations (ATREF, CRYSTAF). These techniques, however, are time consuming. In addition, some semicrystalline polymers undergo cocrystallization, impacting the techniques' universal utility. Adsorption‐based HT‐LC can ideally overcome the limitations of crystallinity‐based separations, shedding new light on the composition of randomly‐polymerized polyolefins. In this report the basic separation capability of the adsorption HT‐LC technique, using a graphitic carbon column, is demonstrated for poly (ethylene‐co‐octene) and poly(ethylene‐co‐propylene) systems and compared with select precipitation/redissolution HT‐LC and ATREF results. Select results in this paper are also compared and contrasted to other recent publications on similar separations of polyolefins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A pH-based method for measuring gaseous ammonia

Cumulative emission or gaseous concentrations of ammonia (NH₃) are commonly measured by trapping gaseous NH₃ in an acidic solution that is later analyzed for total ammonia content. This traditional acid trap method is inexpensive, reliable, and accurate, but it is labor-intensive and inconvenient for high-frequency sampling. This paper describes a new acid trap method in which total ammonia concentration in a citric acid solution is calculated from measured pH by applying a speciation model. With this new method, the quantity of captured ammonia in a single acid trap can be determined repeatedly over time. Testing through titrations, laboratory emission measurements, and field measurement of gaseous NH₃ showed that the method is accurate and reasonably precise. For the most sensitive case standard deviation was 8 μmol kg⁻¹ in titration results, and 10−20 μmol kg⁻¹ in the field trials. The lower quantitation limits from emission measurements and field trials were around 100 and 300 μmol kg⁻¹, respectively. Speciation modeling was used to assess the importance of interferences. Results showed that error due to minor contamination of chemicals and evaporation of water can be kept at low levels. Acidic gases may be a significant interference, but their presence is easy to recognize, and significant error can be avoided by selecting an appropriate acid concentration.     

Evaluation of a robust, diimide-based, porous organic polymer (POP) as a high-capacity sorbent for representative chemical threats

A previously described porous organic polymer (NU-POP-1) was evaluated against four representative chemical threats: ammonia, cyanogen chloride, sulfur dioxide, and octane. Ammonia, cyanogen chloride, and sulfur dioxide are examples of toxic industrial chemicals (TICs) spanning the range from highly basic to strong-acid forming substances, while octane is used to assess physical adsorption capacity. Experiments were carried out using a microbreakthrough test apparatus, which measures the adsorption capacity at saturation and gives an indication of the strength of adsorption. The NU-POP-1 material exhibited substantial removal capabilities against the majority of the toxic chemicals, with capacities as high as or better than an activated, impregnated carbon. The ability to remove the highly volatile toxic chemicals ammonia and cyanogen chloride was intriguing, as these chemicals typically require reactive moieities for removal. The present work presents a benchmark for toxic chemical removal, and future work will focus on incorporating functional groups targeting the toxic chemicals of interest.     

Host Suitability Affects Odor Association in <Emphasis Type="Italic">Cotesia marginiventris</Emphasis>: Implications in Generalist Parasitoid Host-Finding

Insect herbivores often induce plant volatile compounds that can attract natural enemies. Cotesia marginiventris (Hymenoptera: Braconidae) is a generalist parasitoid wasp of noctuid caterpillars and is highly attracted to Spodoptera exigua-induced plant volatiles. The plasticity of C. marginiventris associative learning to volatile blends of various stimuli, such as host presence, also has been shown, but little is known about how this generalist parasitoid distinguishes between host species of varying suitability. Spodoptera exigua is an excellent host that yields high parasitoid emergence, while Trichoplusia ni serves as a sub-optimal host species due to high pre-imaginal wasp mortality. We have found that S. exigua and T. ni induce different volatile blends while feeding on cotton. Here, wind tunnel flight assays were used to determine the importance of differentially induced volatiles in host-finding by C. marginiventris. We found that, while this generalist parasitoid wasp can distinguish between the two discrete volatile blends when presented concurrently, a positive oviposition experience on the preferred host species (S. exigua) is more important than host-specific volatile cues in eliciting flight behavior towards plants damaged by either host species. Furthermore, wasps with oviposition experience on both host species did not exhibit a deterioration in positive flight behavior, suggesting that oviposition in the sub-optimal host species (T. ni) does not cause aversive odor association.     

Comparison of Separations of Fatty Acids from Fish Products Using a 30-m Supelcowax-10 and a 100-m SP-2560 Column

Commercial fish oils and foods containing fish may contain trans and/or isomerized fatty acids (FA) produced during processing or as part of prepared foods. The current American Oil Chemists’ Society (AOCS) official method for marine oils (method Ce 1i-07) is based on separation by use of poly(ethylene glycol) (PEG) columns, for example Supelcowax-10 or equivalent, which do not resolve most unsaturated FA geometric isomers. Highly polar 100-m cyanopropyl siloxane (CPS) columns, for example SP-2560 and CP Sil 88 are recommended for separation of geometric FA isomers. Complementary separations were achieved by use of two different elution temperature programs with the same CPS column. This study is the first direct comparison of the separations achieved by use of 30-m Supelcowax-10 and 100-m SP-2560 columns for fatty acid methyl esters (FAME) prepared from the same fish oil and fish muscle sample. To simplify the identification of the FA in these fish samples, FA were fractionated on the basis of the number and type of double bonds by silver-ion solid-phase extraction (Ag⁺-SPE) before GC analysis. The results showed that a combination of the three GC separations was necessary to resolve and identify most of the unsaturated FA, FA isomers, and other components of fish products, for example phytanic and phytenic acids. Equivalent chain length (ECL) values of most FAME in fish were calculated from the separations achieved by use of both GC columns; the values obtained were shown to be consistent with previously reported values for the Supelcowax-10 column. ECL values were also calculated for the FA separated on the SP-2560 column. The calculated ECL values were equally valid under isothermal and temperature-programmed elution GC conditions, and were valuable for confirmation of the identity of several unsaturated FAME in the fish samples. When analyzing commercially prepared fish foods, deodorized marine oils, or foods fortified with marine oils it is strongly recommended that quantitative data acquired by use of PEG columns is complemented with data obtained from separations using highly polar CPS columns.     

Development of A-scan ultrasound technique for measuring local particle concentration in slurry flows

The effects of solid particle concentration on hydraulic performance and wear need to be considered during the design of slurry transport equipment used in the petroleum and mining industries. The acoustic properties of slurry flows such as velocity, backscatter, and attenuation as a function of volume fraction of solid particles are examined in this study. An ultrasound A-mode imaging method is developed to obtain particle concentration in a flow of soda lime glass particles (diameter of 195 μm) and water slurry in a 0.0254 m diameter pipe. Based on the acoustic properties of the slurry, a technique is developed to measure local solid particle concentrations. The technique is used to obtain concentration profiles in homogeneous (vertical flow) and non-homogeneous (horizontal flow) slurry flows with solid particle concentrations ranging from 1 to 10% by volume using a window size of 0.159 cm. The profiles show average concentration within each window vs. distance from the transducer face. For horizontal flow, profiles are obtained for average flow velocities of 2.0, 3.0, and 3.5 m/s. The algorithm developed utilizes the power spectrum and attenuation measurements obtained from the homogeneous loop as calibration data in order to obtain concentration profiles in other (i.e. non-homogenous) flow regimes. A computational study using FLUENT is performed and a comparison is made with the experimental results. Reasonable agreement between the experimental and computational results is observed. The ultrasound technique has proven to be useful in characterizing slurry flows containing concentrations too high to be investigated using optical techniques.     

Extended studies of degradation mechanisms in the refractory lining of a rotary kiln for iron ore pellet production

Changes, over a period of 8 years, in the chemical composition and morphology of deposit and lining materials in a production rotary kiln for iron ore pellet manufacture are described. The following have been studied: two types of refractory brick used as lining material; deposited chunk materials from the lining; the interaction zones between deposits and linings. Morphological changes at the deposit/lining interface, and the active chemical reactions, are established. Larger hematite grains in the deposit material (5–50 μm) primarily remain at the original deposit/lining interface. The remainder penetrates fissures, voids and brick joints, forms a laminar structure with corundum from the bricks, and migrates in grains in the lining material. Potassium penetrates more deeply into the bricks than hematite, resulting in the formation of kalsilite, leucite and potassium β-alumina, which contribute to degradation of the lining.     

Production of granola breakfast cereal by fluidised bed granulation

In the fluidised bed granulation process the effect of nozzle air pressure and binder spray rate on key aggregate quality attributes were studied. The experimental results show that a decrease in nozzle air pressure leads to larger mean granule size. The combination of lowest nozzle air pressure and lowest binder spray rate results in granules with the highest levels of hardness and crispness. The combination of low nozzle air pressure and low binder spray rate results in the least distribution span. Granola hardness was affected by nozzle air pressure. Nozzle air pressure and binder spray rate did not have significant effect on crispness.     

A designed organic–zeolite hybrid acid–base catalyst

An organic–zeolite hybrid catalyst was synthesised via solid-state impregnation of the zeolite with an amount of melamine corresponding to 20 mol% of the aluminium content. A high density of basic sites is formed in the zeolite. From infrared spectroscopy and TGA measurements we infer that melaminium cations are formed in the zeolite which are highly thermally stable. IR spectroscopic and TGA measurements showed the presence of melaminium after pre-treatment in vacuum at 450 °C. The catalyst exhibited activity in the Knoevenagel condensation reaction between benzaldehyde and ethyl cyanoacetate which is suggested to be promoted by the presence of acid and base sites. The catalyst activity was compared with other known base catalysts including hydrotalcites and magnesium oxide on alumina support.     

Fatigue crack growth and craze-induced crack tip shielding in polycarbonate

This paper expounds a revised characterisation of the elastic stresses ahead of a crack tip in polycarbonate which takes account of the elastic–plastic boundary stresses induced by the presence of the crazed region that surrounds a crack. The advanced experimental techniques used in this work have provided insights into fractography, identification of the crazed region and location of the crack tip position (using confocal laser scanning microscopy and scanning electron microscopy). In addition, the four-parameter model of crack tip stresses has led to modified definitions for crack tip stress intensity factors which explicitly account for craze-induced shielding effects on the fatigue crack growth rate in polycarbonate. The model is generic and offers the potential for increased understanding of fatigue crack growth in polycarbonate.