Fischer–Tropsch synthesis. Compositional changes in an iron catalyst during activation and use

The equilibrium phase compositions of iron have been calculated for gas compositions that could be encountered during the Fischer–Tropsch synthesis. The gas compositions measured experimentally for CO conversion levels in the 30–90% range show that iron should be present as the carbide phase. However, experimental characterization of iron catalysts show that a significant fraction of the iron is present as Fe₃O₄ following synthesis for several days. A model that can account for the experimental catalyst phase composition and the gases present in the reactor would have a core of Fe₃O₄ and an outer layer of iron carbides.     

Curing kinetics and mechanical properties of epoxy nanocomposites based on different organoclays

The effect of different organoclays and mixing methods on the cure kinetics and properties of epoxy nanocomposites based on Epon828 and Epicure3046 was studied. The two kinds of organoclay used in this study, both based on natural montmorillonite but differing in intercalant chemistry, were I.30E (Nanomer I.30E—treated with a long‐chain primary amine intercalant) and C.30B (Cloisite 30B—treated with a quaternary ammonium intercalant, less reactive with epoxy than the primary amine). The two mixing processes used to prepare the nanocomposites were (i) a room‐temperature process, in which the clay and epoxy are mixed at room temperature, and (ii) a high‐temperature process, in which the clay and epoxy are mixed at 120°C for 1 h by means of mechanical mixing. The nanocomposites were cured at room temperature and at high temperature. The quality of dispersion and intercalation/exfoliation were analyzed by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. The heat evolution of the epoxy resin formulation and its nanocomposite systems was measured using differential scanning calorimetry at different heating rates of 2.5, 5, 10, 15, and 20°C min^?1. The cure kinetics of these systems was modeled by means of different approaches. Kissinger and isoconversional models were used to calculate the kinetics parameters while the Avrami model was utilized to compare the cure behavior of the epoxy systems. The cure kinetics and mechanical properties were found to be influenced by the presence of nanoclay, by the type of intercalant, and by the mixing method. POLYM. ENG. SCI., 47:649–661, 2007. © 2007 Society of Plastics Engineers.     

Synthesis and properties of polyimide (containing naphthalene) nanocomposites with organo‐modified montmorillonites

2,7‐Bis(4‐aminophenoxy) naphthalene (BAPN), a naphthalene‐containing diamine, was synthesized and polymerized with a 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) to obtain a polyimide (PI) via thermal imidization. To enhance the thermal and mechanical properties of the polymer, PI–Montmorillonite (MMT) nanocomposites were prepared from a DMAc solution of poly(amic acid) and a DMAc dispersion of MMT, which were organo‐modified with various amounts of n‐dodecylamine (DOA) or cetylpyridium chloride (CPC). FTIR, XRD, and TEM (transmission electron microscopy) were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the organoclay into the PI matrix. Results demonstrated that the introduction of a small amount of MMT (up to 5%) led to the improvement in thermal stability and mechanical properties of PI. The decomposition temperature of 5% weight loss (T_d,5%) in N₂ was increased by 46 and 36°C in comparison with pristine PI for the organoclay content of 5% with DOA and CPC, respectively. The nanocomposites were simultaneously strengthened and toughened. The dielectric constant, CTE, and water absorption were decreased. However, at higher organoclay contents (5–10%), these properties were reduced because the organoclay was poorly dispersed and resulted in aggregate formation. The effects of different organo‐modifiers on the properties of PI–MMT nanocomposite were also studied; the results showed that DOA was comparable with CPC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

A novel synthesis method for the preparation of aromatic poly(imide benzoxazole) from trimellitic anhydride chloride and bis(o‐aminophenol)

A poly(imide benzoxazole) was prepared directly from trimellitic anhydride chloride and 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane (BisAPAF) monomers in a two‐step method. In the first step, a poly(hydroxyamide amic acid) precursor was synthesized by the low‐temperature solution polymerization in an organic solvent. Subsequently, thermal cyclodehydration of the poly(hydroxyamide amic acid) precursor at 350°C produced the corresponding poly(imide benzoxazole). The inherent viscosity of the precursor polymer was 0.22 dL/g. The cyclized poly(imide benzoxazole) showed a glass transition temperature (T_g) at 329°C and a 5% weight loss temperature at 530°C in nitrogen and at 525°C in air. The poly(imide benzoxazole) is amorphous as evidenced by the wide‐angle X‐ray diffraction measurement. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance spectroscopy (¹H NMR). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2388–2391, 2003     

Health benefits of CLA – lessons from pig models in biomedical research

The objective of this review is to highlight the use of pig models for investigating safety, efficacy and the mechanisms of action of conjugated linoleic acid (CLA). Although CLA elicits positive effects in animal models and in vitro systems, a consistent concern in terms of translational research is that the health benefits observed by using these model systems cannot be extrapolated directly into humans. Conversely, the similarities between pigs and humans make the pig an ideal model for examining the health benefits of dietary supplements, functional foods and nutraceuticals. We have developed pig models of viral and bacterial infection to examine the preventive role of dietary CLA supplementation on virally induced immunosuppression and gut health, respectively. Results from these studies indicate that CLA significantly enhances the immune function while limiting the catabolic effects of uncontrolled immune and inflammatory responses. The scientific findings in pig models and human clinical trials demonstrate that CLA modulates immune responses in pigs and humans. Pig models of immunomodulation represent significant improvements over other animal models and in vitro systems because they mimic more closely the compartmentalization of the human immune system and the clinical presentation of human infectious, immune and inflammatory diseases.     

Dynamic mechanical properties and morphology of high‐density polyethylene/CaCO3 blends with and without an impact modifier

Dynamic mechanical analysis and differential scanning calorimetry were used to investigate the relaxations and crystallization of high‐density polyethylene (HDPE) reinforced with calcium carbonate (CaCO₃) particles and an elastomer. Five series of blends were designed and manufactured, including one series of binary blends composed of HDPE and amino acid treated CaCO₃ and four series of ternary blends composed of HDPE, treated or untreated CaCO₃, and a polyolefin elastomer [poly(ethylene‐co‐octene) (POE)] grafted with maleic anhydride. The analysis of the tan δ diagrams indicated that the ternary blends exhibited phase separation. The modulus increased significantly with the CaCO₃ content, and the glass‐transition temperature of POE was the leading parameter that controlled the mechanical properties of the ternary blends. The dynamic mechanical properties and crystallization of the blends were controlled by the synergistic effect of CaCO₃ and maleic anhydride grafted POE, which was favored by the core–shell structure of the inclusions. The treatment of the CaCO₃ filler had little influence on the mechanical properties and morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3907–3914, 2007     

Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Properties of chitosan‐based biopolymer films with various degrees of deacetylation and molecular weights

An increase in the depolymerization of chitosan was found with an increased concentration of sodium perborate. Acetic anhydride was added to reacetylated chitosan in a molar ratio per gulcosamine unit, and the amide I band of IR spectra changed with the addition of acetic anhydride. Sixteen chitosans with various molecular weights (MWs) and degrees of deacetylation (DODs) were prepared. X‐ray diffraction patterns indicated their amorphous and partially crystalline states. Increases in the chitosan MW and DOD increased the tensile strength (TS). TS of the chitosan films ranged from 22 to 61 MPa. However, the elongation (E) of chitosan films did not show any difference with MW. TS of chitosan films decreased with the reacetylation process. However, E of chitosan films was not dependent on DOD. The water vapor permeabilities (WVPs) of the chitosan films without a plasticizer were between 0.155 and 0.214 ng m/m² s Pa. As the chitosan MW increased, the chitosan film WVP increased, but the values were not significantly different. Moreover, the WVP values were not different from low DOD to high DOD. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3476–3484, 2003     

Novel method for preparation of quaternary ammonium ionomer from epoxidized styrene–butadiene–styrene triblock copolymer and its use as compatibilizer for blending of styrene–butadiene–styrene and chlorosulfonated polyethylene

A novel method for the preparation of a quaternary ammonium ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed by a ring‐opening reaction of epoxidized SBS with triethylamine hydrochloride in the presence of a phase transfer catalyst. The optimum conditions were studied. The ionomer was characterized by quantitative analysis, IR spectroscopy, and ¹H‐NMR spectroscopy. Its water absorbency, oil absorbency, dilute solution viscosity, and use as a compatibilizer for the blending of SBS and chlorosulfonated polyethylene (CSPE) were investigated. The results showed that, under optimum conditions, the epoxy groups can be completely converted to the quaternary ammonium groups. The IR spectrum did not exhibit the absorption peak for quaternary ammonium groups, whereas the ¹H‐NMR spectrum and titration method demonstrated it. With increasing ionic group content, the water absorbency of the ionomer increased whereas its oil absorbency decreased. These indicated the amphiphilic character of the SBS ionomer. The dilute solution viscosity of the ionomer in toluene/methanol (9/1) solvent increased with increasing quaternary ammonium group content. The ionomer was used as a compatibilizer for the blends of SBS and CSPE. The addition of a small amount of the ionomer to the blend enhanced the mechanical properties of the blends: 2 wt % ionomer based on the blend increased the tensile strength and ultimate elongation of the blend nearly 2 times. The blends of equal parts SBS and CSPE behaved as oil‐resistant thermoplastic elastomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1975–1980, 2006     

Methods to determine solubility parameters of polymers at high temperature using inverse gas chromatography

Experimental values of Flory–Huggins parameters, χ, between polymers and probes, are frequently used to determine the solubility parameters of the polymers by the method of DiPaola–Baranyi and Guillet. The solubility parameters of probes were usually estimated by using heat of vaporization. When χ is measured at a temperature near the critical temperature of the probes and used to determine the solubility parameter of polymers, the departure of enthalpy of the probe vapor from the ideal gas state should be considered. This study discussed the method to make the correction and its effect on the determination solubility parameter of polymers. Without correction in the vapor phase enthalpy, the solubility parameters of the probes and polymer tend to be underestimated and the error increases when the critical temperature is approaching. Analytical expressions for the effect of correction on the solubility parameter of probes and parameters of polymers were derived. By use of probes with a range of solubility parameters on both sides of the solubility parameter of polymers, the correlation between parameters of polymers was shown to be reduced. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1547–1555, 2004