Degradation mechanism of polystyrene sulfonic acid membrane and application of its composite membranes in fuel cells

The lifetime behavior of a H-2/O-2 proton exchange membrane (PEM) fuel cell with polystyrene sulfonic acid (PSSA) membrane have been investigated in order to give an insight into the degradation mechanism of the PSSA membrane. The distribution of sulfur concentration in the cross section of the PSSA membrane was measured by energy dispersive analysis of X-ray, and the chemical composition of the PSSA membrane was characterized by infrared spectroscopy before and after the lifetime experiment. The degradation mechanism of the PSSA membrane is postulated as: the oxygen reduction at the cathode proceeds through some peroxide intermediates during the fuel cell operation, and these intermediates have strong oxidative ability and may chemically attack the tertiary hydrogen at the a carbon of the PSSA; the degradation of the PSSA membrane mainly takes place at the cathode side of the cell, and the loss of the aromatic rings and the SO3- groups simultaneously occurs from the PSSA membrane. A new kind of the PSSA-Nafion composite membrane, where the Nafion membrane is bonded with the PSSA membrane and located at the cathode of the cell, was designed to prevent oxidation degradation of the PSSA membrane in fuel cells. The performances of fuel cells with PSSA-Nafion101 and PSSA-recast Nafion composite membranes are demonstrated to be stable after 835 h and 240 h, respectively.

Zodiac算法新的Square攻击

该文重新评估了Zodiac算法抗Square攻击的能力。Zodiac算法存在8轮Square区分器,该文首先根据算法的结构特性,给出了Zodiac的4个等价结构,而后利用等价结构得到了两个新的9轮Square区分器。利用新的区分器,对不同轮数的Zodiac算法实施了Square攻击,对12轮,13轮,14轮,15轮和16轮Zodiac的攻击复杂度分别为237.3,262.9,296.1,2137.1和2189.5次加密运算,选择明文数分别为210.3,211,211.6,212.1和212.6。结果表明:完整16轮192bit密钥的Zodiac算法是不抗Square攻击的。

一种基于排队论的DoS攻防绩效评估方法

提出了一种新的基于排队论的DoS攻防绩效评估方法.针对不同种类DoS攻防手段建立了统一的指标体系和绩效计算方法,基于排队论方法分别建立评估模型,对UDP Flood和SYN Flood攻击的绩效进行不包含主观因素的定量评估,分析不同攻击手段和强度的有效性.针对典型DoS攻防场景,利用网络仿真工具进行模拟,通过实验与模型推导结果对比验证了排队论模型的合理性,并阐述了此方法在不同类型DoS攻防手段中的应用.

33轮SHACAL-2的差分非线性攻击

利用SHACAL-2的一个17轮差分非线性区分器,结合被猜测子密钥空间分割的方法和快速傅立叶变换,提出了一种攻击33轮SHACAL-2的新方法.该方法攻击33轮SHACAL-2需要244的选择明文、2496.6的33轮SHACAL-2加密和2502次算术运算,攻击成功概率为99%.与已有的结果相比较,新攻击有效地提高了单密钥下SHACAL-2的攻击轮数.

Hot-corrosion behaviors of overlay-clad yttria-stabilized zirconia coatings in contact with vanadate-sulfate salts

A dense clad overlay with chemical inertness was achieved on top of the plasma-sprayed YSZ thermal barrier coatings by laser in order to protect them from hot-corrosion attack. The Al2O3-clad YSZ coating exhibited good hot-corrosion behavior in contact with salt mixture of vanadium pentoxide (V2O5) and sodium sulfate (Na2SO4) for a longtime of 100 h at 1173 K. The LaPO4-clad YSZ coating showed corrosion resistance inferior to the Al2O3-clad one. Yttria was leached from YSZ by reaction between Y2O3 and V2O5, which caused progressive destabilization transformation of YSZ from tetragonal (t) to monoclinic (m) phase. The chemical inertness of the clad layers and the restrained infiltration of the molten corrosive salts by the dense clad layers were primary contributions to improvement of the hot-corrosion resistances.

Double propagation based on diepoxide, a facile route to high molecular weight poly(propylene carbonate)

Poly(propylene carbonate) (PPC) with number average molecular weight (M-n) higher than 200 kg/mol was prepared via the terpolymerization of carbon dioxide, propylene oxide and diepoxide using Y(CCl3OO)(3)-ZnEt2-glycerine coordination catalyst. When equimolar ZnEt2 and diepoxide were used, double propagation active species were generated in situ by nucleophilic attack of metal alkoxide on diepoxide, leading to PPC of doubled M-n value. The molecular weight of PPC has dramatic influence on its thermal and mechanical performances. PPC with M of 227 kg/mol showed modulus of 6900 MPa, while the modulus of PPC with M-n of 109 kg/mol was only 4300 MPa. Moreover, when M-n increased from 109 to 227 kg/mol, a 37 degrees C increase of the onset degradation temperature was observed.

Studies of catalyzed reaction mechanism between co-polyether (THF/EO) and N-100 by NMR - Interaction and complex formation between reactants and catalysts

To elucidate the mechanism of the catalyzed reaction of co-polyether (EO/THF) with N-100, the interaction and complex formation between reactants and catalysts were investigated by means of NMR spectroscopy. It is shown that the resonance peak of isocyanate carbon splits into two parts when the solutions of N-100 and co-polyether were mixed. The disappearing of proton resonance peak of hydroxyl group in NMR spectra when dibutyltin dilaurate(DBTDL) were added to the copolyether(THF/EO) solution indicates the complex formation, This interaction appears to be a bonding of tin to the oxygen of hydroxyl and make the hydrogen of the hydroxyl group very mobile and active, then exchange with other protons, In the case of triphenyl bismuth(TPB), the high field shift and intensity enhancement of proton peak were observed, which suggest a nucleophilic attack of the bismuth to the hydroxyl hydrogen.

Chromatographic separation and C-13 NMR characterization of aromatic diester-diacids isomers

Reverse phase high performance liquid chromatography (HPLC) was used to separate and quantify aromatic diester-diacids isomers which arise from the opening selectivity of anhydride rings towards methanol. C-13 NMR spectroscopy was a supplementary tool to characterize the isomer structure. It was found that a meta-position attack is slightly preferred in pyromellitic dianhydride (PMDA), while the preferred position of an attack in bridged dianhydrides is determined by the chemical nature (donors or accepters) of the bridged group. The stronger its electron-withdrawing abilities, the lower the probability of a meta-position attack.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF BENZOYL PEROXIDE - A RADICAL AROMATIC-SUBSTITUTION RESULTING IN BIPHENYLCARBOXYLIC ACID IN THE GAS-PHASE

A radical aromatic substitution resulting in biphenylcarboxylic acid is inferred for the decomposition of benzoyl peroxide from the chemical ionization and collision-induced dissociation mass spectra. The thermolysis of benzoyl peroxide gives rise to a benzoyloxy radical, which undergoes rapid decarboxylation and hydrogen abstraction leading to phenyl radical and benzoic acid, respectively. Attack of the resulting phenyl radical on the benzoic acid results in bipbenylcarboxylic acid. On the other hand, the phenyl radical abstracts a hydrogen atom to yield benzene, which is then subjected to the attack of a benzoyloxy radical, affording phenyl benzoate. This substitution reaction rather than the recombination of benzoyloxy and phenyl radicals is found to be responsible for the formation of phenyl benzoate under the present conditions.

Cannibalism in Japanese flounder juveniles, Paralichthys olivaceus, reared under controlled conditions

Laboratory experiments were conducted to determine the effects of sand substratum, light, starvation, fish density and size variation on cannibalism among Japanese flounder juveniles, Paralichthys olivaceus. Cannibalistic behavior (biting and swallowing) increased significantly with starvation except in darkness, where juveniles could not find and attack their prey. Cannibalism occurred more frequently in heterogeneous than in the homogeneous size groups. Cannibalism was more frequent in light than in darkness at each starvation level. With sufficient food present, sand had no significant effect on cannibalism among homogeneous size juveniles, but played an important role in discouraging predation among members of the heterogeneous size groups. With sufficient food present, the rate of cannibalism was generally low and there were no significant differences in cannibalism among fish density levels of the homogeneous juveniles, With starvation, the cannibalism rate was significantly higher in high density groups than in the lower ones. Our results indicate that size variation, starvation and Light are the major factors affecting cannibalism in flounder juveniles, while sand and fish density only have a limited effect on cannibalism, depending on the nature of other factors. (C) 2000 Elsevier Science B.V. All rights reserved.

Feeding behaviour of Japanese flounder larvae under laboratory conditions

Tank-reared Japanese flounder larvae, Paralichthys olivaceus, had a major feeding peak in the morning and a secondary peak in the afternoon throughout the larval development, with light being the primary factor regulating their feeding activity. The larvae consumed rotifers in preference to Artemia for up to 10 days, after which the food preference shifted to Artemia. Feeding rates of the larvae prior to 10 days post-batch depended on prey density, but in the old larvae, feeding rates were independent of prey density. Maximum feeding rate occurred at 19 degrees C. The occurrence of the attack posture, after its onset at first feeding (2 days post-hatch), increased up to 25 days, began to decrease when the larvae prepared to settle down, then disappeared after settlement. The occurrence frequency of the attack posture was positively related to fish density, but inversely related to starvation duration, and occurred most frequently at 19 degrees C. This posture depended on prey density in larvae prior to 10 days post-hatch, but became independent of prey density as the larvae developed. It was obvious that, for flounder larvae, attack posture was a behavioural character closely related to feeding and subject to larval development and environmental factors. (C) 2000 The Fisheries Society of the British Isles.

Corrosion behaviour of steel in beach soil along Bohai Bay

Research on corrosion of steel structures in various marine environments is essential to assure the safety of structures and can effectively prolong their service life. In order to provide data for anticorrosion design of oil exploitation structures in the Bohai Bay, the corrosion behaviour and properties of steel in beach soil, using typical steel samples (Q235A carbon steel and API 5Lx52 pipeline steel) buried 0.5, 1.0 and 1.5 m deep under typical beach soils in Tanggu, Yangjiaogou, Xingcheng, Yingkou and Chengdao for 1-2 years were studied. The carbon steel and pipeline steel were both corroded severely in the beach soil, with the form of corrosion being mainly uniform with some localised attack (pitting corrosion). The corrosion rate of the carbon steel was up to 0.16 mm/year with a maximum penetration depth of 0.76 mm and that of the pipeline steel was up to 0.14 mm/year, with a maximum penetration depth of 0.53 mm. Compared with carbon steel, the pipeline steel generally had better corrosion resistance in most test beach soils. The corrosion rates and the maximum corrosion depths of carbon steel and pipeline steel were in the order: Tanggu>Xingcheng>Chengdao>Yingkou>Yangjiaogou with corrosion altering with depth of burial. The corrosion of steel in the beach soil involves a mixed mechanism with different degrees of soil aeration and microbial activity present. It is concluded that long term in situ plate laying experiments must be carried out to obtain data on steel corrosion in this beach soil environment so that the effective protection measures can be implemented.

中国大陆及邻区地震活动背景、环境触发与地震预测研究

This dissertation that includes most of the P. PH.D research work during 2001~2002 covers the large-scale distribution of continental earthquakes in mainland China, the mechanism and statistic features of grouped strong earthquakes related to the tidal triggering, some results in earthquake prediction with correlativity analysis methods, and the flushes from the two strong continental earthquakes in South Asia in 2001. Mainland China is the only continental sub-plate that is compressed by collision boundaries at its two sides, within which earthquakes are dispersive and distributed as seismic belts with different widths. The control capability of the continental block boundaries on the strong earthquakes and seismic hazards is calculated and analyzed in this dissertation. By mapping the distribution of the 31282 ML:3s2,0 earthquakes, I found that the depth of continental earthquakes depend on the tectonic zonings. The events on the boundaries of relatively integrated blocks are deep and those on the new-developed ruptures are shallow. The average depth of earthquakes in the West of China is about 5km deeper than that in the east. The western and southwestern brim of Tarim Basin generated the deepest earthquakes in mainland China. The statistic results from correlation between the grouped M7 earthquakes and the tidal stress show that the strong events were modulated by tidal stress in active periods. Taking Taiwan area as an example, the dependence of moderate events on the moon phase angles (￡>) is analyzed, which shows that the number of the earthquakes in Taiwan when D is 50° ,50° +90° and 50° +180° is more than 2 times of standard deviation over the average frequency at each degree, corresponding to the 4th, 12th and 19th solar day after the new moon. The probability of earthquake attack to the densely populated Taiwan island on the 4th solar day is about 4 times of that on other solar days. On the practice of earthquake prediction, I calculated and analyzed the temporal correlation of the earthquakes in Xinjinag area, Qinghai-Tibet area, west Yunnan area, North China area and those in their adjacent areas, and predicted at the end of 2000 that it would be a special time interval from 2001 to 2003, within which moderate to strong earthquakes would be more active in the west of China. What happened in 2001 partly validated the prediction. Within 10 months, there were 2 great continental earthquakes in south Asia, i.e., the M7.8 event in India on Jan 26 and M8.1 event in China on Nov. 14, 2001, which are the largest earthquake in the past 50 years both for India and China. No records for two great earthquakes in Asia within so short time interval. We should speculate the following aspects from the two incidences: The influence of the fallacious deployment of seismic stations on the fine location and focal mechanism determination of strong earthquakes must be affronted. It is very important to introduce comparative seismology research to seismic hazard analysis and earthquake prediction research. The improvement or changes in real-time prediction of strong earthquakes with precursors is urged. Methods need to be refreshed to protect environment and historical relics in earthquake-prone areas.