Effect of pH on microbial hydrogen fermentation

The influence of initial pH of the culture medium on hydrogen production was studied using sucrose solution and a mixed microbial flora from a soybean‐meal silo. Hydrogen production was not observed at pH values of 3.0, 11.0 and 12.0 but low production was observed at pH values 5.0 and 5.5. The pH of the experimental mixture decreased rapidly and produced hydrogen gas within 30 h. Methane was not detected at initial pH values between 6.0 and 10.0. The sucrose degradation efficiency increased as the initial pH value increased from 3.0 to 9.0. The maximum sucrose degradation efficiency of 95% was observed at pH 9.0. The maximum specific production yields of hydrogen, VFAs and alcohols were 126.9 cm³ g^?1 sucrose (pH of 9.0), 0.7 gCOD g^?1 sucrose (pH of 8.0) and 128.7 mgCOD g^?1 sucrose (pH of 9.0), respectively. The relationship between the hydrogen ion concentration and the specific hydrogen production rate has been mathematically described. The best kinetic parameters on the specific hydrogen production rate were K_OH = 1.0 × 10^?7 mol dm^?3 and K_H = 1.1 × 10^?4 mol dm^?3 (r² = 0.86). The maximum specific hydrogen production rate was 37.0 cm³ g^?1 VSS h^?1. © 2002 Society of Chemical Industry     

Catalytic Behavior of Bis(Pyrrolide-Imine) and Bis(Phenoxy-Imine) Titanium Complexes for the Copolymerization of Ethylene with Propylene, 1-Hexene,or Norbornene

This contribution reports the catalytic behavior of bis(pyrrolide-imine)Ti complexes 1 and 2 , [2-(RNCH)-C₄H₃N]₂TiCl₂ ( 1 , R = Ph; 2 , R = cyclohexyl), and bis(phenoxy-imine)Ti complex 3 , [2-(Ph-NCH)-3-t Bu-C₆H₃O]₂TiCl₂ for the copolymerization of ethylene with propylene, 1-hexene, or norbornene. An inspection of the X-ray structures of complexes 1–3 suggested that complexes 1 and 2 with pyrrolide-imine ligands would provide more space for olefin polymerization than complex 3 with phenoxy-imine ligands. In addition, DFT calculations also showed that active species derived from complexes 1 and 2 possess higher electrophilicity of the Ti center compared to that from complex 3 . Complexes 1 and 2 on activation with methylalumoxane (MAO) had higher affinity for propylene and 1-hexene and incorporated higher amounts of propylene ( 1 ; 30.5 mol%, 2 ; 23.4 mol%) and 1-hexene ( 1 ; 1.9 mol%, 2 ; 1.7 mol%) than complex 3 (propylene; 4.5 mol%, 1-hexene; 0.4 mol%). The incorporation levels of propylene and 1-hexene displayed by complexes 1 and 2 were lower than those for Cp₂TiCl₂ (propylene; 41.6 mol%, 1-hexene; 5.1 mol%) under identical conditions. In contrast, complexes 1 and 2 exhibited higher incorporation ability for norbornene and produced copolymers with much higher norbornene contents ( 1 ; 32.0 mol%, 2 ; 26.5 mol%) than Cp₂TiCl₂ (1.2 mol%) under the same conditions. Additionally, complex 3 also promoted higher norbornene incorporation (4.3 mol%) than Cp₂TiCl₂ and provided a copolymer with extremely narrow molecular weight distribution (M_w/M_n 1.14). A correlation exists between electrophilicity of the Ti center in active species and norbornene incorporation.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Synthesis and Magneto-mechanical Properties of Ce-TZP/La M-Type Hexaferrite Composite

An in situ composite composed of ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP) and La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was synthesized from a powder mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO. The dense Ce-TZP dispersed with platelike La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ crystals as a second phase were formed after sintering from 1250° to 1350°C. The saturation magnetization of the in situ composite Ce-TZP/La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was proportional to the mass fraction of the hexaferrite second phase in Ce-TZP. The coercivity of the composite with a 20 mass% of second phase decreased from 9.14 to 2.52 kOe (from 728 to 201 kA/m) after the pulverization of the composite. The susceptibility (χ) increased by 15%–25% under uniaxial stress on the composite. The change of the susceptibility (Δχ/χ) value increased with decreasing the mass fraction of the second phase in the composite. The Δχ was found to increase linearly with applied stress and abruptly change on cracking, which is expected for the application in fracture sensing of the composite.     

Mirror Constant for Tyranno® Silicon-Titanium-Carbon-Oxygen Fibers Measured in Situ in a Three-Dimensional Woven Silicon Carbide/Silicon Carbide Composite

The strength, S , of ceramic and glass fibers often can be estimated from fractographic investigation using the fracture mirror radius, r _m, and the relationship S = A _m/( r _m)^1/2, where A _mis the "mirror constant." The present work estimates the value of A _mfor Tyranno^® Si-Ti-C-O fibers in situ in a three-dimensional woven SiC/SiC-based composite to be 2.50 ± 0.09 MPa·m^1/2. This value is within the range of 2–2.51 MPa·m^1/2 previously obtained for nominally similar Nicalon^® Si-C-O fibers.     

Mixed powder coating film using thermoplastic polyester and its alkaline resistance

To improve alkaline resistance, a newly mixed powder coating film using thermoplastic polyethylene terephthalate (PET) was investigated. Two kinds of polyvinyl butyral (PVB) and two kinds of polyamide (PA) were chosen as the secondary polymer. The melting temperatures (T _ms) of these materials were lower than that of primary PET polymer so the mixed powder coating was able to form a dual phase film through a fluidized bed coating process. Microscope and Fourier transform infrared spectroscopy (FTIR) observations revealed that the dual phase structure was indeed successfully formed and there was a secondary layer over the entire surface area of the film. This mixed powder coating film significantly enhanced the alkaline resistance to an environment filled with NaOH solution at 40°C in which a secondary material would be effective in protecting the film. With regard to both alkaline resistance and film formability, PET/PVB was superior to the PET/PA mixture.     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

Shape memorizing properties of a hydrogel of poly(vinyl alcohol)

Hydrogel prepared by repetitive freezing and thawing of poly(vinyl alcohol) aqueous solution was chemically crosslinked with glutaraldehyde. The chemically crosslinked hydrogel hardly changed its physical appearance, and showed good elasticity and strength as original gel. However, after treating in boiling water, it swelled a little, depending on the condition of the chemical treatment. The melted gel thus obtained showed shape memorizing property, that is, it could firmly hold nearly 200% of strain, keeping its original high elasticity. The strain could be released very quickly (< 1 s) in boiling water, and the gel was suggested to be applied to a new type of gel actuator. X-ray diffraction study revealed that the melted gel does not necessarily reform the physical crosslinks in exactly the same manner as the original gel in the process of shape restoring, but the distribution of the physical crosslinks can be restored as they were. It was suggested that the chemical crosslinks which remember the distribution of the physical crosslinks plays a critical roll in the shape restoring process.     

Pervaporation membranes for ethanol–water mixture prepared by plasma polymerization. III. Perfluorocarbon membranes

Pervaporation membranes for the ethanol–water mixture were prepared by plasma polymerization of tetrafluoroethylene, perfluoropropane, and perfluoropropylene onto porous substrates. The influence of the monomers on the elemental ratio (F/C) of the polymer depositions by X-ray photoelectron spectroscopy was rather small compared with that of the W/FM parameter (W = wattage for plasma excitation, FM = mass flow rate of a monomer). The optical emission spectroscopy indicated the similarity of gaseous species formed in the plasmas. The membranes were found ethanol-permselective, showing separation coefficients (α_EtOH) around 4–7 and a wide range of permeation rates (J), 10–10^?2 kg/m² h, for the 4.8 wt % ethanol solution at 40°C. The α_EtOH of the membranes with thicker depositions could be correlated to the F/C ratios as a measure of membrane hydrophobicity. It was thought that, by making a plot α_EtOH against J values for the perfluorocarbon membranes, they could be classified into three groups on thickness of deposition. The ethanol-separation mechanisms for each group, which may contain four kinds of mass transfer schemes, i.e., distillation through larger pores, flow of sorption layer at the liquid–membrane interface, and diffusions through deposition or substrate, were also discussed.     

Thermal shock resistance of flat plastic integrated circuit packages

Flat packages (FPs) were formed from epoxy molding compounds with various physical properties using a transfer molding machine. The compounds were prepared by changing kinds and amounts of additives and addition methods. The thermal shock test was carried out by the following procedures. The plastic package was soaked alternately in liquid nitrogen (?196°) and in liquid solder (200°) in the cycle of 140s. The median life to crack initiation was defined to be the cycles when half of the specimens exhibited crack initiation. According to linear fracture mechanics, the following expression was obtained relating the median life N, thermal stress σ_t, and strength σ_b; N = C/σ·(σ_b/σ_t)^m. We found the linear relation between logarithm of Nσ and logarithm of σ_b/σ_t for various packages, and estimated the values of C and m as 5 × 10⁴ MPa² and 5.5, respectively. The value of m was the same as that obtained for a dual-in-line package.