Fuel properties and emissions of soybean oil esters as diesel fuel

The effects of using blends of methyl and isopropyl esters of soybean oil with No. 2 diesel fuel were studied at several steady-state operating conditions in a four-cylinder turbocharged diesel engine. Fuel blends that contained 20, 50, and 70% methyl soyate and 20 and 50% isopropyl soyate were tested. Fuel properties, such as cetane number, also were investigated. Both methyl and isopropyl esters provided significant reductions in particulate emissions compared with No. 2 diesel fuel. A blend of 50% methyl ester and 50% No. 2 diesel fuel provided a reduction of 37% in the carbon portion of the particulates and 25% in the total particulates. The 50% blend of isopropyl ester and 50% No. 2 diesel fuel gave a 55% reduction in carbon and a 28% reduction in total particulate emissions. Emissions of carbon monoxide and unburned hydrocarbons also were reduced significantly. Oxides of nitrogen increased by 12%.     

Nanocomposites from poly(ethylene-co-methacrylic acid) ionomers: effect of surfactant structure on morphology and properties

A detailed study of the structure-property relationships for nanocomposites prepared using melt processing techniques from a sodium ionomer of poly(ethylene-co-methacrylic acid) and a series of organoclays is reported. Transmission electron microscopy, X-ray scattering, stress-strain behavior, and Izod impact analysis were used to evaluate the nanocomposite morphology and physical properties. Four distinct surfactant structural effects lead to improved levels of exfoliation and higher stiffness for these nanocomposites: higher number of alkyl tails on the amine rather than one, longer alkyl tails instead of shorter ones, use of 2-hydroxy-ethyl groups as opposed to methyl groups on the ammonium ion, and an excess amount of the amine surfactant on the clay instead of an equivalent amount. These trends are opposite of what has been seen in nylon 6 based nanocomposites but are similar to those observed in nanocomposites formed from LDPE and LLDPE. Although some organoclays were exfoliated better than others, none of the ionomer-based nanocomposites exhibited exfoliation levels as great as those seen in nylon 6 nanocomposites; nevertheless, these nanocomposites offer promising improvements in performance and may be particularly interesting for barrier applications.     

Solid state magnetic resonance spectra of Illinois No. 6 coal and some reductive alkylation products

Illinois No. 6 coal and its reductive methylation and butylation products have been studied by magnetic resonance techniques. Conventional CP-MAS¹³Cn.m.r. spectroscopy indicates that 62% of the carbon atoms in the coal are aromatic and that about 6% of the carbon atoms are carbonyl. Esters are more abundant than carboxylic acids. The resonances of methoxy groups and other novel etheric carbon atoms are apparent in the high field region. Dipolar dephasing experiments suggest that methyl carbon atoms constitute no more than 16% of the carbon, methylene and methine carbon atoms about 14% and quaternary aliphatic carbon atoms about 2%. The dipolar dephasing experiments in conjunction with previous work also permit estimates of the hydrogen atom distribution. The THF-insoluble products obtained in the reductive alkylation reactions with¹³C-enriched alkylating agents contain paramagnetic and ferromagnetic substances that adversely influence the solid state n.m.r. spectra. However, good ¹³C n.m.r. spectra were obtained after these substances were extracted with aqueous hydrochloric acid. The O:C alkylation ratios are 1.2 and 1.0 for methylation and butylation, respectively. Dipolar dephasing experiments establish that the decay constants of functional groups in the whole coal and of C- and O-methyl-¹³C and C- and O-butyl-1 -¹³C nuclei in the labelled coal molecules are very similar to those of reference compounds. These findings suggest that the decay constants measured for the ¹³C nuclei in coals and coal-derived solids provide reliable information about their degree of substitution.     

Response to walnut olfactory and visual cues by the parasitic wasp Diachasmimorpha juglandis

Diachasmimorpha juglandis is a specialist parasitoid attacking fly larvae in the genus Rhagoletis that feed exclusively on walnut fruit husks. In a free-foraging assay comparing response to uninfested, infested, and mechanically damaged fruits, we first determined that D. juglandis use host feeding damage on the fruit as a cue for host presence. In another free-foraging assay that used artificial walnut models and wind tunnel experiments, D. juglandis distinguished infested from uninfested fruits by using either olfactory or visual cues separately. However, the response rate of wasps in the wind tunnel was raised considerably when visual cues were also available. We analyzed the volatile compounds emitted by cohorts of uninfested, mechanically damaged, and infested fruits 1, 3, 5, 8, and 10 days after oviposition by flies into the infested fruits. Total volatile emissions did not differ significantly among treatments, but quantitative changes in volatiles distinguished infested fruits from uninfested and damaged fruits. The fact that parasitoids did not distinguish between infested and damaged fruits in assays where damage was visible indicates that they rely on visual cues when those are available.     

Intercalation and exfoliation of clay nanoplatelets in epoxy‐based nanocomposites: TEM and XRD observations

Diglycidyl ether of bisphenol A (DGEBA) and diglycidyl ether of bisphenol F (DGEBF) reinforced with organo‐montmorillonite clay nanoplatelets were investigated using anhydride‐ and amine‐curing agents. The sonication technique was used to process epoxy/clay nanocomposites. The basal spacing of clay nanoplatelets was observed by wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS) techniques, and transmission electron microscopy. It was found that the basal spacing of clay nanoplatelets in epoxy matrix was expanded after mixing with either DGEBA/DGEBF or methyltetrahydrophthalic‐anhydride (MTHPA) curing agent. The sonication technique provided larger d‐spacing of clay nanoplatelets. Because of the different curing temperatures, MTHPA‐cured epoxy/clay nanocomposites produced more expanded d‐spacing of clay nanoplatelets modified with methyl, tallow, bis(2‐hydroxyethyl) quaternary ammonium (MT2EtOH) than triethylenetetramine‐cured nanocomposites. Depending on the selection of curing agent and organic modification for clay nanoplatelets, the d‐spacing was expanded to be up to 8.72 nm. POLYM. ENG. SCI., 46:452–463, 2006. © 2006 Society of Plastics Engineers     

Isolation and characterization of ganglioside 9-O-acetyl-GD3 from bovine buttermilk

Bovine buttermilk contains a unique ganglioside, 9-O-acetyl-GD₃. In order to isolate large quantities of this ganglioside, a simplified isolation scheme which consists of several ion-exchange and silica gel column chromatographic procedures was devised. The isolated 9-O-acetyl-GD₃ was characterized on the basis of its thin-layer chromatographic behavior, its immunoreactivity with a specific monoclonal antibody, JONES, and by conversion to authentic GD₃ by mild base treatment.     

Electrophilic Aromatic Functionalization of Phenolic Photoresist Polymers

Summary Functionalization of both linear poly(4-hydroxystyrene) (PHS) and branched poly(4-hydroxystyrene) (PHS-B) was accomplished via a Reimer-Tiemann electrophilic aromatic substitution reaction. Linear and branched poly(4-hydroxystyrene-co-5-vinylsalicylaldehyde) (pHS/5VSA and pHS-B/5VSA) copolymers were observed to undergo acid-catalyzed, novolac type self-crosslinking. Both the pHS/5VSA and pHS-B/5VSA copolymer systems possessed a lower deep ultra violet microlithographic sensitivity compared to linear PHS when formulated in negative photoresists. The sluggishness of the negative photoresists containing 5-vinylsalicylaldehyde functionalized copolymers was attributed to a combination of resonance stabilization and steric hindrance effects.     

Effect of organoclay structure on nylon 6 nanocomposite morphology and properties

A carefully selected series of organic amine salts were ion exchanged with sodium montmorillonite to form organoclays varying in amine structure or exchange level relative to the clay. Each organoclay was melt-mixed with a high molecular grade of nylon 6 (HMW) using a twin screw extruder; some organoclays were also mixed with a low molecular grade of nylon 6 (LMW). Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the effect of amine structure on nanocomposite morphology and physical properties. Three surfactant structural issues were found to significantly affect nanocomposite morphology and properties in the case of the HMW nylon 6: decreasing the number of long alkyl tails from two to one tallows, use of methyl rather than hydroxy-ethyl groups, and use of an equivalent amount of surfactant with the montmorillonite, as opposed to adding excess, lead to greater extents of silicate platelet exfoliation, increased moduli, higher yield strengths, and lower elongation at break. LMW nanocomposites exhibited similar surfactant structure-nanocomposite behavior. Overall, nanocomposites based on HMW nylon 6 exhibited higher extents of platelet exfoliation and better mechanical properties than nanocomposites formed from the LMW polyamide, regardless of the organoclay used. This trend is attributed to the higher melt viscosity and consequently the higher shear stresses generated during melt processing.     

Processing and physical properties of native grass-reinforced biocomposites

Big blue stem grass fiber-reinforced high density polyethylene powder biocomposites were fabricated using two separate processing schemes: (1) by compounding biofiber with the thermoplastic powder in an extruder and subsequently injection molding the extrusion pellets and (2) by combining biofiber and the powder thermoplastic powder using a modified sheet molding compounding (SMC) line and subsequently compression molding the sheet material. The physical properties including storage modulus, heat deflection temperature (HDT), notched Izod impact strength, and morphology were evaluated with dynamic mechanical analysis, Izod impact strength measurement, and microscopy observation. It was found that compression-molded specimens achieved similar modulus values to injection molded specimens for grass-reinforced high density polyethylene (HDPE) composites. The stiffness of the compression-molded specimens is related to the consolidation state of the samples, which depends on compression molding conditions such as temperature, pressure, and mold type. Compression-molded specimens exhibited a higher HDT and notched Izod impact strength compared to injection-molded samples. Grass fiber-reinforced cellulose acetate butyrate (CAB) biocomposites made with SMC processing had similar physical properties with grass fiber-reinforced HDPE composites, which indicates that natural fiber-reinforced CAB biocomposites have the potential to replace polyolefin-based composites for automotive applications. POLYM. ENG. SCI. 47:969–976, 2007. © 2007 Society of Plastics Engineers.     

Efficiency of mineral admixtures in mortars: Quantification of the physical and chemical effects of fine admixtures in relation with compressive strength

This work is the fourth part of an overall project the aim of which was the development of general mix design rules for concrete containing different kinds of mineral admixtures. The two first parts presented the separation and quantification, by means of an empirical model based on semi-adiabatic calorimetry measurements, of the different physical effects responsible for changes in cement hydration (short terms) when chemically inert quartz powders were used in mortars. Part three dealt with an intensive experimental program, presenting and commenting more than 2000 compressive strength measurements. This program concerned 1 day to 6 months old mortars containing up to 75% of inert and pozzolanic admixtures. All these compressive strength results are analyzed in this fourth part and the influence of three effects, namely dilution, heterogeneous nucleation and the pozzolanic effect, are discriminated and quantitatively evaluated. An efficiency concept is proposed in order to take into account the effect of mineral admixture in mortars from both the physical and chemical points of view. It uses an efficiency function ξ(p) that has notable properties: it is independent of time, independent of fineness and independent of the type of mineral admixture.