Aqueous electrochemical intercalation of bromine into graphite fibers

For the first time, graphite fibers have been electrochemically intercalated with Br⁻ that have the same structure and properties as those intercalated from vapor phase Br₂. This was accomplished by intercalating pitch-based Thornel^® K-1100 graphite fibers at low temperature (near 0 °C) and high currents (2 A) for long times (6 h). The mechanism appears to be that Br⁻ is oxidized to aqueous Br₂ which, when sufficient local concentration builds up, intercalates the fiber. This was confirmed by intercalating K-1100 fiber in a saturated aqueous Br₂ solution without passing an electrical current. The applied voltage does apparently lower the activation energy of the reaction as evidenced by the observation that P-120 and P-100 fibers will not intercalate in aqueous Br₂ unless a voltage is applied.     

Static and dynamic mechanical properties of a kenaf fiber–wood flour/polypropylene hybrid composite

A natural fiber hybrid composite containing equal proportions of kenaf fibers (KFs) and wood flour (WF) as the reinforcements and polypropylene (PP) as the polymer matrix was prepared, and its static and dynamic mechanical properties were compared with KF/PP and WF/PP composites. Static tensile and flexural tests and dynamic mechanical analysis (DMA) were carried out. The hybrid composite exhibited tensile and flexural moduli and strength values closer to those of the KF composite, which indicated a higher reinforcing efficiency of KFs compared with WF. DMA revealed that although the glass‐transition temperature remained unchanged by the replacement of half of the WF by KFs, the α‐transition temperature of the hybrid composite was identical to that of WF composite. The magnitudes of both the α and β (glass) transitions of the hybrid composite were comparable to that of the WF/PP composite. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 665–672, 2005     

Effect of H2O adsorption on the electrical transport properties of double-walled carbon nanotubes

Water molecules adsorbed on a double-walled carbon nanotube (DWCNT) serve as charge trapping centers when present in low density and as electron donors when present in high density. There is a discontinuous change between the low- and high-density regions. H₂O molecules are apt to be adsorbed on the outer surface of DWCNTs, and in this case the electrical transport properties are extremely sensitive to environment, which suggests that DWCNTs are hole doped and act as an electric dipole with the inner tube.     

Structural, electrical and magnetic properties of carbon-nickel composite thin films

Carbon-nickel composite thin films (600 nm thick) were prepared by dc magnetron sputtering of Ni and C at several temperatures (25-800 °C) on oxidized silicon substrates. By transmission electron microscopy it was found that the composite consisted of Ni (or Ni₃C) nanoparticles embedded in a carbon matrix. The metallic nanoparticles were shaped in the form of globular grains or nanowires (of the aspect ratio as high as 1:60 in the sample prepared at 200 °C). The carbon matrix was amorphous, or graphite-like depending on deposition temperature. At low deposition temperatures T_S (25-400 °C) the Ni₃C nanoparticles were of hcp phase. Samples prepared at T_S ? 600 °C contained ferromagnetic fcc Ni nanoparticles. A correlation was found between the structural, electrical and magnetic properties of the composites. To characterise the films, dependences, such as resistivity vs. temperature, current vs. voltage, differential conductivity vs. bias voltage, and magnetoresistivity, were determined. For example, the tunneling effect was found in samples in which the metallic nanoparticles were separated by 2-3 nm thick amorphous carbon. When the metallic nanoparticles were connected by graphite-like carbon regions (having a metallic conductivity, in contrast to a-C), the temperature coefficient of the resistivity became slightly positive. An anisotropic magnetoresistivity of ∼0.1% was found in the sample that contained ferromagnetic columnar fcc Ni. Zero magnetoresistivity was found in the sample in which the metallic nanoparticles were of non-magnetic hcp phase.     

Preparation and characterization of modified starch‐based plastic film reinforced with short pulp fiber. II. Mechanical properties

Native corn starch‐ and hydroxypropylated starch (HPS‐) based plastic films were prepared using the short pulp fiber as the reinforcement and the glycerol as the plasticizer. The results of tensile test showed that the strain and stress at break and elastic modulus increased with pulp content. With glycerol content, the strain at break increased considerably, but the breaking stress and elastic modulus decreased. And the stress–strain curves showed that the brittleness problem of films was overcome by the pulp, glycerol, and water content. The hydroxypropyl starch films showed results similar to those of the native starch films. The results of the three‐point bending test showed that maximum deflection, flexural strength, and specific work increased with pulp content, but the flexural modulus was the highest at a pulp content of 20%. And with the glycerol content, the maximum deflection and specific work of rupture increased, but the bending elastic modulus decreased. The hydroxypropyl starch films showed results similar to those of native starch films as far as the maximum deflection and flexural strength were concerned, but the bending elastic modulus and specific work of the hydroxypropyl starch films were considerably lower than those of starch films. So it was concluded that the flexibility of films was improved by the hydroxypropylation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2108–2117, 2003     

Miscibility and carbon dioxide transport properties of poly(3-hydroxybutyrate) (iPHB) and its blends with different copolymers of styrene and vinyl phenol

This work summarizes the miscibility and transport properties of different polymer blends obtained by mixing a bacterial, isotactic poly(3-hydroxybutyrate) (iPHB) with copolymers of styrene and vinyl phenol (Sty-co-VPh copolymers). Given that iPHB and pure commodity poly(styrene) (PS) form immiscible blends, PS has been modified by copolymerizing it with vinyl phenol (VPh) units, in an attempt to promote blend miscibility. VPh units have appropriate functional groups that interact with iPHB ester moieties. The potential miscibility was investigated by differential scanning calorimetry (DSC) measuring the glass transition temperatures of blends of different compositions. As an additional test, the interaction parameter between the two components, using the iPHB melting point depression caused by the second component, was also measured. Copolymers containing less than 90% styrene showed miscibility with iPHB.Given the remarkable barrier properties of iPHB to gases and vapours, the study has been completed by measuring transport properties of carbon dioxide through different iPHB/Sty-co-VPh copolymer blends, using gravimetric sorptions in a Cahn electrobalance. A clear difference was observed between the behaviour of rubbery blends and those that exhibit a glassy behaviour at the selected experimental temperature (303 K).     

Determination of the adhesion force between particles and a flat surface, using the centrifuge technique

By using a centrifuge technique, the influence of powdery material particle size on the adhesion force particle-surface was determined. In order to achieve this, the adhesion of phosphatic rock (ρ_p = 3.090 kg m^− 3) and of manioc starch particles (ρ_p = 1.480 kg m^− 3) on a steel surface were studied. A microcentrifuge that reached a maximum speed rotation of 14000 rpm and which contained specially designed centrifuge tubes was used. There tubes contained the flat surface where the test particles were deposited. The powder particles were dispersed on these disks and the particles detachment were performed using diverse centrifugal speeds. The graphics of particle percentages still adhering on the surface of the disks as a function of the applied detachment force showed that the profile of adhesion force followed a log-normal distribution. The adhesion force increased with particle size. The manioc starch particles presented adhesion forces greater than those for the phosphatic rock particles for all particle sizes studied. The results obtained were compared with the theory proposed by Derjaguin, Muller and Toporov whose theoretical adhesion presented values close to the experimental data for the phosphatic rock particles adhesion on the stainless steel surface. On the contrary, the theoretical values were lower than the experimental ones for the manioc starch particles maybe due to the small roughness of these particles, their physical properties (softer and deformable material) and/or specific chemical interactions since the organic composition of the manioc starch particles that can dominate the adhesion force. Finally, the separation distance among the surfaces in contact (Z₀) was estimated in approximately 1.0 × 10^− 9 m for the phosphatic rock and 5.0 × 10^− 10 m for the manioc starch. These results were weakly dependent on the particle size range.     

Metal effects in the Fischer-Tropsch synthesis: Bond-order-conservation-morse-potential approach

We have applied the BOC-MP method to theoretically analyze the metal effects in the Fischer-Tropsch (FT) synthesis by calculating the energetics of conceivable elementary steps (the relevant heats of chemisorption and the reaction activation barriers) during CO hydrogenation over the periodic series Fe(110), Ni(111), Pt(111), Cu(111). The basic steps such as dissociation of CO, hydrogenation of carbidic carbon, C-C chain growth by insertion of CH₂ versus CO into the metal-alkyl bonds, and chain termination leading to hydrocarbons (alkanes versus -olefins) or oxygenates are discussed in detail. It is shown that the periodic trends in the ability of metal surfaces to dissociate chemical bonds and those to recombine the bonds are always opposite. In particular, we argue that metallic Fe is necessary to produce the abundance of carbidic carbon from CO but the synthesis of hydrocarbons and oxygenates can effectively proceed only on carbided Fe surfaces which resemble the less active metals such as Pt. More specifically, we project that the C-C chain growth should occur predominantly via CH₂ insertion into the metal-alkyl bond and the primary FT products should be -olefins. These and other model projections are in agreement with experiment.     

HPCS-AM-DAC共聚物的合成及絮凝性能研究

以羟丙基壳聚糖(HPCS)、丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)为原料合成三元高分子共聚物(HPCS-AM-DAC)。采用FTIR、1HNMR、XRD、SEM对其结构和形貌进行了表征。考察了反应温度、引发剂硝酸铈铵用量、单体滴加时间及DAC用量对产物阳离子度及特性黏数的影响。结果表明,在水为25 mL、丙烯酰胺为2 g、HPCS为1 g、反应温度70℃、引发剂用量为1.7%(以HPCS质量为基准,下同)、单体滴加时间为35min、DAC为3.5g的条件下,产物的阳离子度和特性黏数均达到较佳值,分别为63.01%和468.81mL/g。采用壳聚糖(CTS)、HPCS、HPCS-AM-DAC及市售阳离子聚丙烯酰胺(CPAM)对高岭土模拟废水进行絮凝实验,考察了絮凝体系pH、不同絮凝产品投加量对浊度去除率的影响。结果表明,在浊度为200NTU的高岭土模拟废水中,HPCS-AM-DAC絮凝的适宜pH为2～6,适宜投加量为2～5 mg/L,在该条件下浊度去除率均在96%以上。     

2,2￠,6,6￠-四甲基-4,4￠-二苯氧基二苯砜、二苯醚和对苯二甲酰氯三元无规共聚物的合成与表征

以2,2￠,6,6￠-四甲基-4,4￠-二苯氧基二苯砜(o-M2DPODPS)、二苯醚(DPE)和对苯二甲酰氯(TPC)为单体，在无水AlCl3和N,N-二甲基甲酰胺(DMF)存在的条件下，于1,2-二氯乙烷(DCE)中进行低温溶液无规共缩聚，合成了一系列新型线型高分子量含双邻甲基取代结构的聚醚砜醚酮酮(DM-PESEKK)/聚醚酮酮(PEKK)无规共聚物，并用IR, DSC, XRD, TGA和1H-NMR等方法对共聚物进行了表征分析，考察了共聚物的溶解性能. 结果表明，随着DM-PESEKK含量的增加，玻璃化转变温度(Tg)逐渐升高，熔融温度(Tm)逐渐降低，结晶度下降，溶解性得到明显改善.