Decomposition kinetics and recycle of binary hydrogen‐tetrahydrofuran clathrate hydrate

Decomposition kinetics and recycle of hydrogen–tetrahydrofuran (H₂–THF) clathrate hydrates were investigated with a pressure decay method at temperatures from 265.1 to 273.2 K, at initial pressures from 3.1 to 8.0 MPa, and at stoichiometric THF hydrate concentrations for particle sizes between 250 and 1000 μm. The decomposition was modeled as a two‐step process consisting of H₂ diffusion in the hydrate phase and desorption from the hydrate cage. The adsorption process occurred at roughly two to three times faster than the desorption process, whereas the diffusion process during formation was slightly higher (ca. 20%) than that during decomposition. Successive formation and decomposition cycles showed that occupancy seemed to decrease only slightly with cycling and that there were no large changes in hydrate structure due to cycling. Results provide evidence that the formation and decomposition of H₂ clathrate hydrates occur reversibly and that H₂ clathrate hydrates can be recycled with pressure. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Determination of traction-separation laws on an acrylic adhesive under shear and tensile loading

Structural acrylic adhesives are of special interest because those adhesives are cured at room temperature and can be bonded to oily substrates. To use those adhesives widely for structural bonding, it is necessary to clarify the methodology for predicting strengths of bonding structures with those adhesives. Recently, cohesive zone models (CZMs) have been receiving intensive attentions for simulation of fracture strengths of adhesive joints, especially when bonded with ductile adhesives. The traction-separation laws under mode I and mode II loadings require to estimate fracture toughness of adhesively bonded joints. In this paper, the traction-separation laws of an acrylic adhesive in mode I and mode II were directly obtained from experiments using Arcan type adhesively bonded specimens. The traction-separation laws were determined by simultaneously recording the J-integral and the opening displacements in the directions normal and tangential to the adhesive layer, respectively.     

Chemical‐Free Approach for Z‐Isomerization of Lycopene in Tomato Powder: Hot Air and Superheated Steam Heating above the Melting Point of Lycopene

Z‐isomers of lycopene exhibit higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. Therefore, it is important to develop an efficient and environmentally friendly procedure for Z‐isomerization. The current methods for Z‐isomerization of (all‐E)‐lycopene use toxic chemicals such as organic solvents and catalysts. This study is aimed to develop a chemical‐free method for Z‐isomerization of (all‐E)‐lycopene in tomato powder by hot air and superheated steam heating. The Z‐isomerization reaction is promoted by heating above the melting point of lycopene. When heated with superheated steam, the thermal decomposition of lycopene is suppressed compared to that when heated with hot air. When tomato powder is heated at 240 °C for 5 min by superheated steam, the total Z‐isomer content and remaining lycopene are 69.0% and 90.7%, respectively, while with hot air heating, the total Z‐isomer content and remaining lycopene are 69.9% and 68.0%, respectively. These results indicate that the thermal Z‐isomerization of lycopene occurs in the molten state and heating in a low oxygen atmosphere suppresses the thermal decomposition of lycopene. Practical Applications: Tomato powder rich in lycopene Z‐isomers is an important ingredient for the food and animal feed industries. Since Z‐isomers of lycopene are more soluble in solvents including ethanol which is a low‐toxicity and environmentally friendly solvent, the efficiency of lycopene extraction with ethanol can be improved by using the Z‐isomer‐rich tomato powder as a raw material. The obtained Z‐isomer‐rich extract has a high added value because the Z‐isomers have higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. In addition, since lycopene Z‐isomers exhibit higher accumulation efficiency and better color improvement in hen egg yolks than those of the all‐E‐isomer, Z‐isomer‐rich tomato powder is an effective animal feed.     

采用MAMMOS技术的高密度光记录

MAMMOS(Magnetic Amplifying Magneto－ Optical System:磁畴扩大磁光系统 )是实现高密度磁光盘的有效方法。不仅能得到不依赖于磁畴长度的较大的读出信号振幅,而且还能实现超出光学系统衍射极限的分辨率。过去,为实现磁畴的复印与扩大,要对记录膜面施加垂直方向的外部磁场。而现在得知,同时施加垂直磁场和水平方向的磁场,可大幅度地提高微小磁畴的读出特性。确认采用施加水平磁场的方法,在λ =635 nm, NA=0.55的条件下, 0.15μ m的连续磁畴也能获得 BER=2× 10－ 4的读出效果。     

The effects of Ni and Li doping on the performance of lithium manganese oxide material for lithium secondary batteries

Layered Li_0.7[M_1/6Mn_5/6]O₂ (M=Li, Ni) was synthesized using a sol-gel method. P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor was first synthesized by a sol-gel method, and then O2-Li_0.7[M_1/6Mn_5/6]O₂ was prepared by an ion exchange of Li for Na in P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor. From charge/discharge curves, it was seen that Li_0.7[Li_1/6Mn_5/6]O₂ has two plateaus similar to those observed from a spinel structure, but Li_0.7[Ni_1/6Mn_5/6]O₂ holds a single plateau as observed from a typical layered structure. It was considered that Li_0.7[Li_1/6Mn_5/6]O₂ undergoes a phase transformation from layered to spinel structure during the charge/discharge cycle, but Li_0.7[Ni_1/6Mn_5/6]O₂ maintains O2-layered structure after the cycles. Li_0.7[Ni_1/6Mn_5/6]O₂ was higher in discharge capacity and retention rate than Li_0.7[Li_1/6Mn_5/6]O₂.     

Alteration of substrate specificity of cholesterol oxidase from Streptomyces sp. by site-directed mutagenesis

Despite the structural similarities between cholesterol oxidasefrom Streptomyces and that from Brevibacterium, both enzymesexhibit different characteristics, such as catalytic activity,optimum pH and temperature. In attempts to define the molecularbasis of differences in catalytic activity or stability, substitutionsat six amino acid residues were introduced into cholesteroloxidase using site-directed mutagenesis of its gene. The aminoacid substitutions chosen were based on structural comparisonsof cholesterol oxidases from Streptomyces and Brevibacterium.Seven mutant enzymes were constructed with the following aminoacid substitutions: L117P, L119A, L119F, V145Q, Q286R, P357Nand S379T. All the mutant enzymes exhibited activity with theexception of that with the L117P mutation. The resulting V145Qmutant enzyme has low activities for all substrates examinedand the S379T mutant enzyme showed markedly altered substratespecificity compared with the wild-type enzyme. To evaluatethe role of V145 and S379 residues in the reaction, mutantswith two additional substitutions in V145 and four in S379 wereconstructed. The mutant enzymes created by the replacement ofV145 by Asp and Glu had much lower catalytic efficiency forcholesterol and pregnenolone as substrates than the wild-typeenzyme. From previous studies and this study, the V145 residueseems to be important for the stability and substrate bindingof the cholesterol oxidase. In contrast, the catalytic efficiencies(k_cat/K_m) of the S379T mutant enzyme for cholesterol and pregnenolonewere 1.8- and 6.0-fold higher, respectively, than those of thewild-type enzyme. The enhanced catalytic efficiency of the S379Tmutant enzyme for pregnenolone was due to a slightly high k_catvalue and a low K_m value. These findings will provide severalideas for the design of more powerful enzymes that can be appliedto clinical determination of serum cholesterol levels and assterol probes.     

Knoop Microhardness Anisotropy and the Indentation Size Effect on the Basal Plane of Single-Crystal Alumina (Sapphire)

The Knoop microhardness anisotropy profile was determined for the basal plane of a Czochralski grown alumina single crystal for indentation test loads from 100 through 1000 g. Microhardness maxima occur at low indentation test loads for the long axis of the Knoop indenter parallel to the 〈2[Onemacr][Onemacr]0〉. Minima exist for the long axis parallel to the 〈10[Onemacr]0〉. This low indentation test load profile is attributed to slip on the primary slip system, the (0001)〈[Onemacr][Onemacr]20〉, as previously noted by Brookes and co-workers. The degree of the microhardness anisotropy decreases for higher indentation test loads. This results from the activation of multiple slip systems to accommodate the greater amounts of plastic flow required by the larger indentation sizes. The microhardness profile becomes more uniform with increasing indentation test load until the Knoop microhardness approaches a test-load-independent, orientation-independent microhardness of 1167 ± 34 kg/mm². The indentation size effect (ISE) was further investigated through lubricated indentation hardness measurements. Lubrication of the test specimen surface significantly reduces the ISE. Results indicate that friction between the test specimen surface and the indenter facets is a major portion of the ISE.     

Morphological study by TEM on uniaxially oriented thin films of PET, PEN and their blends

Uniaxially oriented thin films of poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) and their blends were prepared by applying shear strain to their respective melts, and the resulting morphologies were studied by transmission electron microscopy. Selected-area electron diffraction of each film revealed well-defined uniaxial orientation of polymer chains in the shearing direction. In the uniaxially oriented thin film of PEN, stacked-lamellar structure with the average long period of 27 nm consisting of a crystalline region about 15 nm thick and an amorphous one about 12 nm thick was found here and there in the dark-field image: PEN-type. On the other hand, stacked-lamellar structure was rarely observed in the case of PET: PET-type. In PET/PEN blends, the morphologies changed from the PET-type to the PEN-type with increasing content of PEN.     

Effect of particle size distribution of fly ash-cement system on the fluidity of cement pastes

This paper investigates the effect of particle size distribution of fly ash-cement system on the fluidity of the cement pastes using class F fly ash collected from the hopper attached to an electrostatic precipitator when the burning conditions and types of coal are changed at a coal-fired power plant. The unburned carbon content of fly ashes used in the experiment is less than 1.5%. To prevent the unburned carbon in fly ashes from affecting the fluidity of the pastes, polycarboxylic acid plasticizer with more saturation amount is added into the pastes for experimentation. The particle size distribution of fly ash-cement system is analyzed using n value of Rosin-Rammler function and the n value is derived with a nonlinear least squares fitting method. As the result, it is shown that the fluidity increases as the particle size distribution becomes wider, i.e., as n value gets smaller.