Behavior of 316L stainless steel containing corrosion pits under cyclic loading

The environmental performance of 316L grade stainless steel, in the form of tensile specimens containing a single corrosion pit with various aspect ratios, under cyclic loading in aerated chloride solutions is investigated in this study. Results from environmental tests were compared and contrasted with those obtained using finite element analysis (FEA). Fractography of the failed specimens obtained from experiments revealed that fatigue crack initiation took place at the base of the shallow pit. The crack initiation shifted towards the shoulder and the mouth of the pit for pits of increasing depth. This process is well predicted by FEA, as the strain contour maps show that strain is the highest around the centric strip of the pit. However, for shallow pits, local strain is uniformly distributed around that strip but begins to concentrate more towards the shoulder and the mouth region for increasingly deep pits.     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.     

Physical Stability of Octenyl Succinate–Modified Polysaccharides and Whey Proteins for Potential Use as Bioactive Carriers in Food Systems

The high cost and potential toxicity of biodegradable polymers like poly(lactic‐co‐glycolic)acid (PLGA) has increased the interest in natural and modified biopolymers as bioactive carriers. This study characterized the physical stability (water sorption and state transition behavior) of selected starch and proteins: octenyl succinate–modified depolymerized waxy corn starch (DWxCn), waxy rice starch (DWxRc), phytoglycogen, whey protein concentrate (80%, WPC), whey protein isolate (WPI), and α‐lactalbumin (α‐L) to determine their potential as carriers of bioactive compounds under different environmental conditions. After enzyme modification and particle size characterization, glass transition temperature and moisture isotherms were used to characterize the systems. DWxCn and DWxRc had increased water sorption compared to native starch. The level of octenyl succinate anhydrate (OSA) modification (3% and 7%) did not reduce the water sorption of the DWxCn and phytoglycogen samples. The Guggenheim–Andersen–de Boer model indicated that native waxy corn had significantly (P < 0.05) higher water monolayer capacity followed by 3%‐OSA‐modified DWxCn, WPI, 3%‐OSA‐modified DWxRc, α‐L, and native phytoglycogen. WPC had significantly lower water monolayer capacity. All Tg values matched with the solid‐like appearance of the biopolymers. Native polysaccharides and whey proteins had higher glass transition temperature (Tg) values. On the other hand, depolymerized waxy starches at 7%‐OSA modification had a “melted” appearance when exposed to environments with high relative humidity (above 70%) after 10 days at 23 °C. The use of depolymerized and OSA‐modified polysaccharides blended with proteins created more stable blends of biopolymers. Hence, this biopolymer would be suitable for materials exposed to high humidity environments in food applications.     

Prediction of brittle-to-ductile transitions in polystyrene

In this study it is attempted to predict brittle-to-ductile transitions (BDTs) in polystyrene blends, induced either by an increase in temperature or by a decrease in inter-particle distance. A representative, two-dimensional volume element (RVE) of a polystyrene matrix with 20% circular voids, is deformed in tension. During deformation a hydrostatic-stress based craze-nucleation criterion [1] is evaluated. The simulations demonstrate that crazes initiate at low temperatures while a transition from crazing to shear yielding (BDT) is found around 75 °C. The numerical results correlate well with tensile tests on similar heterogeneous polystyrene. The presence of an absolute length, as experimentally found, is more difficult to explain. Near a free surface a T_g-depression is measured for polystyrene and also the resistance to indentation in polystyrene is lower than expected from bulk properties. Both observations are rationalised by an enhanced segmental mobility of chains near a free surface. As a consequence of these findings, an absolute length-scale could be incorporated in the numerical simulations. For simplicity, the length-scale is modelled by taking a temperature gradient over a thin layer near the internal free surfaces of the RVE. Deformation of the RVE with different absolute length-scales shows that indeed also the experimentally found brittle-to-ductile transition can be predicted if the ligament thickness between the inclusions (‘voids’) in polystyrene is below a critical value of ca. 15 nm.     

井下乳化/水热催化裂解复合降黏开采稠油技术研究

实验考察了胜利孤东稠油井下催化水热裂解和乳化/催化水热裂解降黏效果。所用催化剂为水溶性铁镍钒体系,Fe3+∶Ni2+∶VO4+=5∶1∶1,100 g稠油与30 g 0.5%催化剂水溶液在240℃反应24小时。原始黏度(50℃)11.0和8.36 Pa.s的两种稠油裂解并静置除水后,黏度降低76.2%和75.6%,室温放置60天后降黏率下降小于3个百分点,气相色谱显示裂解后轻组分明显增加,红外光谱显示稠油组分发生脱羧反应且芳环数减少。讨论了稠油催化水热裂解反应机理。所用化学助剂JN-A在油水中均可溶,耐温达250℃,耐矿化度达50 g/L,其水溶液以30∶100的质量比与稠油混合时形成低黏度的O/W乳状液。当水相含1.0%JN-A和0.5%催化剂时,两种稠油水热裂解后的反应混合物为O/W乳状液,黏度仅为319和309 mPa.s,静置除水后的稠油降黏率增加到86.5%和87.3%,其中的轻组分含量进一步增加。该井下乳化/催化水热裂解复合降黏法成功地用于孤东两口蒸汽吞吐井,稠油井作业后初期采出的原油黏度由~9 Pa.s降低到1 Pa.s左右,随采油时间延长而逐渐升高,约50天后超过4Pa.s。图2表6参5。     

Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

Effect of oxygen deficiency (δ) on transition temperature of yttrium cuprate superconductors

The nature of pairing mechanism as well as transition temperature of yttrium cuprates is discussed using the strong coupling theory. An interaction potential has been developed for the layered structure with two conducting CuO₂(a–b) layers in a unit cell. The interaction potential properly takes care of electron-electron, electron-phonon and electron-plasmon interactions. Furthermore, the electron-phonon coupling parameter (λ), the modified Coulomb repulsive parameter (μ*) and the 2D acoustic phonon (plasmon) energy as a function of oxygen deficiency is worked out. Finally, the superconducting transition temperature (T _c) is then evaluated by using these coupling parameters and obtainedT _c = 95(92)K for Y(Yb)Ba₂Cu₃O_7−δ superconductors withδ = 0·0. The model parameters estimated from the layered structure approach are consistent with the strong coupling theory. The result deduced on the variation ofT _c withδ are in fair agreement with the earlier reported data on yttrium cuprates. The analysis of the above results are discussed.     

Biodegradation of monoaromatic hydrocarbons in aquifer columns amended with hydrogen peroxide and nitrate

The ability of indigenous microorganisms to degrade benzene, toluene, ethylbenzene and xylenes (BTEX) in laboratory scale flow-through aquifer columns was tested separately with hydrogen peroxide (110 mg/l) and nitrate (330 mg/l as NO₃⁻) amendments to air-saturated influent nutrient solution. The continuous removal of individual components from all columns relative to the sterile controls provided evidence for biodegradation. In the presence of hydrogen peroxide, the indigeneous microorganisms degraded benzene and toluene (> 95%), meta- plus para-xylene (80%) and ortho-xylene (70%). Nitrate addition resulted in 90% removal of toluene and 25% removal of ortho-xylene. However, benzene, ethylbenzene, meta- and para-xylene concentrations were not significantly reduced after 42 days of operation. Following this experiment, low dissolved oxygen (< 1 mg/l) conditions were initiated with the nitrate-amended column influent in order to mimic contaminated groundwater conditions distal from a nutrient injection well. Toluene continued to be effectively degraded (> 90%), and more than 25% of the benzene, 40% of the ethylbenzene, 50% of the meta- plus para-xylenes and 60% of the ortho-xylene were removed after several months of operation.