Crystallization and Si incorporation mechanisms of SAPO-34

In this study of the synthesis of SAPO-34 molecular sieves, XRD, SEM, XRF, IR and NMR techniques were applied to monitor the crystalloid, structure and composition changes of the samples in the whole crystallization process in order to get evidence for the crystallization as well as Si incorporation mechanism of SATO-34. XRD results revealed that the crystallization contained two stages. In the first 2.5 h (the earlier stage), high up to similar to80% of relative crystallinity could be achieved and the crystal size of SAPO-34 was almost the same as that of any longer time, indicating a fast crystallization feature of the synthesis. In this stage, IR revealed that the formation of SAPO-34 framework structure was accompanied by the diminution of hydroxyls, suggesting that crystal nuclei of SAPO-34 may arise from the structure rearrangement of the initial gel and the condensation of the hydroxyls. NMR results reveal that the template and the ageing period are crucial for the later crystallization of SAPO-34. Preliminary structure units similar to the framework of SAPO-34 have already formed before the crystallization began (0 h and low temperature). Evidence from IR, NMR, and XRF shows that the formation of the SAPO-34 may be a type of gel conversion mechanism, the solution support and the appropriate solution circumstance are two important parameters of the crystallization of SAPO-34. Meanwhile, NMR measurements demonstrated that about 80% of total Si atoms directly take part in the formation of the crystal nuclei as well as in the growth of the crystal grains in the earlier stage (<2.5 h). Evidence tends to support that Si incorporation is by direct participation mechanism rather than by the Si substitution mechanism for P in this stage (<2.5 h). In the later stage (>2.5 h), the relative content of Si increased slightly with a little decrease of Al and P. The increase of Si(4Al) and the appearance of the Si(3Al), Si(2Al), Si(1Al) and Si(OAl) in this stage suggest that substitution of the Si atoms for the phosphorus and for the phosphorus and aluminum pair takes place in the crystallization. The relationship among structure, acidity and crystallization process is established, which suggests a possibility to improve the acidity and catalytic properties by choosing a optimum crystallization time, thus controlling the number and distribution of Si in the framework of SAPO-34. (C) 2002 Elsevier Science Inc. All rights reserved.

Ti_(0.17)Zr_(0.08)V_(0.34)Nb_(0.01)Cr_(0.1)Ni_(0.3)氢化物电极合金微观结构及电化学性能研究

采用XRD、FESEM-EDS、ICP及EIS等方法研究了Ti0.17Zr0.08V0.34Nb0.01Cr0.1Ni0.3氢化物电极合金微观结构和电化学性能。X射线衍射分析表明:该合金由体心立方结构(bcc)的V基固溶体主相和少量六方结构的C14型Laves相组成;FESEM及EDS分析表明:V基固溶体主相形成树枝晶,C14型Laves相呈网格状围绕着树枝晶的晶界,元素在两相中的分布呈现镜像关系。电化学性能测试结果表明:该合金的氢化物电极在303￣343K较宽的温度区间内,表现出较高的电化学容量,在303K和343K时,电化学容量分别为337.0mAh·g-1和327.9mAh·g-1。在303K循环100周后,容量为282.7mAh·g-1。ICP分析结果表明,氢化物电极在充放电循环过程中,V及Zr元素向KOH电解质中的溶出较为严重。EIS研究表明,金属氢化物电极表面电化学反应的电荷转移电阻(RT)随循环次数的增加而增加,相应的交换电流密度则随循环次数的增加而降低。氢化物电极循环过程中RT的增大以及V和Zr元素的溶解,可能是导致电极容量衰减的主要原因。

过量氮和磷引起的富营养化对海水无机碳源汇强度的影响

过量氮和磷引起的海水富营养化引起了一系列的生态环境效应，探讨二者的耦合关系对阐明全球海洋生态环境变化机制意义重大。本论文首次探讨了过量氮和磷引起的富营养化对海水无机碳体系的影响，通过室内系统模拟实验，构筑了过量氮和磷与无机碳体系变化的定量耦合关系，在此基础上获得了中国近海典型海域特别是南黄海近十年氮和磷演变引起的无机碳源汇格局变化，获得了以下一系列新的结果和认识： 1、不同营养盐（NO3-、NH4+、NO2-和PO43-）对水体溶解无机碳体系均有重要影响，且影响程度有较大的差异。 在模拟实验中，当NO3-<188 μmol/L，NH4+<126 μmol/L，NO2-<39.5 μmol/L时均可明显提高水体的固碳能力，相应水体中的DIC、HCO3-和 pCO2均较空白对照组时有一定程度的下降。当N浓度达到一定值后，其固碳能力减弱，DIC、HCO3-和pCO2出现相反变化。当NH4+>126 μmol/L和NO2->39.5 μmol/L时pCO2增加，向大气释放CO2。在PO43-添加组中，当浓度小于19.5μmol/L时DIC、pCO2较空白对照组下降，水体表现为大气CO2的汇，其固碳能力高于N组。在孔石莼添加组中，各营养盐组水体的固碳能力均高于空白对照组，相应水体中DIC、HCO3-和pCO2的下降明显。其中，同一营养盐浓度水平下，NH4+组中各无机碳组分的变化幅度明显高于NO3-和NO2-组，PO43-组的无机碳体系变化幅度低于N组。其中，当NO3-、NH4+和NO2-浓度分别在71 μmol/L，49.7 μmol/L和11.7 μmol/L时，pCO2下降明显，水体表现为大气CO2的强汇。对无机碳各参数的变化量与营养盐进行多元回归分析，得到以下统计关系： ⊿DIC=-0.937(⊿PO43-)-0.34(⊿NO3-)-0.46(⊿NH4+)+0.11(⊿NO2-)（R2=0.69, n=30，Sig.<0.05） ⊿HCO3-=-1.357(⊿PO43-)-0.35(⊿NO3-)-0.57(⊿NH4+)-0.013(⊿NO2-)（R2=0.76, n=32, Sig.<0.05） ⊿CO32-=0.344(⊿PO43-)+0.16(⊿NO3-)+0.18(⊿NH4+)+0.076(⊿NO2-)（R2=0.69, n=32, Sig.<0.05） ⊿pCO2=-1.321(⊿PO43-)-0.12(⊿NO3-)-0.31(⊿NH4+)-0.032(⊿NO2-)（R2=0.84, n=35, Sig.<0.01） 2．氮、磷对海水无机碳体系的源汇格局影响主要受控于水体浮游藻类对营养盐的利用。 模拟实验各种情况下Chl-a的浓度均有不同程度的变化。在N组中，当NH4+<126 μmol/L，随着NH4+浓度的增加，Chl-a浓度增加，而高浓度（NH4+>126 μmol/L）的实验组中，Chl-a则随浓度的增加而下降。当NO2-和PO43-的浓度分别大于39.5 μmol/L和19.5 μmol/L时，水体中Chl-a随营养盐浓度的增加而出现下降趋势，不同的是NO3-添加组在实验浓度范围内藻类均出现了不同程度的增长，这可能与浮游藻类对过量营养盐的耐受性不同有关。在低浓度时，PO43-组pCO2的下降最为明显，这与 PO43-组Chl-a的含量较高相一致，其次为NH4+，NO3-高于NO2-，可见在实验水体中PO43-对于藻类新陈代谢作用影响明显，从而作用到无机碳上的影响也就最为明显。对各实验水体⊿Chl-a与无机碳各组分作相关性分析发现，⊿Chl-a与⊿pCO2的相关性最为明显（R2=0.75，p<0.0001），这可能是因为浮游藻类光合作用和分解作用消耗或生成的首先是海水中的游离CO2（即pCO2）。在孔石莼组中，由于大藻对过量营养盐的耐受性较强，因此各组中藻类干重均有一定程度的增长。藻类干重的增加以NH4+最为明显，其次为NO3-和NO2-，这可能与其对N盐的优先吸收顺序NH4+>NO3->NO2-有关。加PO43-组中藻类的干重增加量低于NH4+和NO3-组，这与大藻的生理特性有关。对藻类干重增加量⊿m与⊿DIC作相关性发现，二者相关性明显（R2=0.64，p<0.01），这是由于孔石莼光合作用同时吸收HCO3-和CO2为碳源有关。 3、近年来，中国近海由于海水过量氮磷引起的富营养化，可使大部分海域海水无机碳汇强度增加 应用室内模拟获得的无机碳与氮、磷之间的定量耦合关系，估算了过量氮、磷引起的富营养化条件下，中国近海水体无机碳源汇的变化情况。结果表明，近十年来，由于氮、磷浓度的增加而导致渤海、南黄海、北黄海和东海每年从大气中多吸收0.197×106t C、0.302×106t C、0.039×106t C和2.233×106t C，东中国近海营养要素的含量的变化及组成比例的时间性和地区性差异是造成各海区碳通量差异的重要因素；对2006年南黄海水文、化学、生物与无机碳体系之间的相互关系进行综合分析，可知水体无机碳体系与营养盐水平密切相关。

Effect of Cl- on the corrosive wear of AISI 321 stainless steel in H2SO4 solution

The effect of Cl- on the corrosive wear behaviour of AISI 321 stainless steel in H2SO4 solution was studied via the corrosive wear rate, the load bearing capacity of passive film and the relationship between pitting and corrosive wear. There is a critical load at natural potential, below which the corrosive wear rate is slightly lowered by Cl-, while above which is increased. At natural potential there are more pits at low load than that at a higher one in the wear tracks and the pits are also deeper. The load bearing capacity is lowered by Cl- at passive region and then the corrosive wear rate increased.

Stress corrosion cracking of AISI 321 stainless steel in acidic chloride solution

The stress corrosion cracking (SCC) of LambdaISI 321 stainless steel in acidic chloride solution was studied by slow strain rate (SSR) technique and fracture mechanics method. The fractured surface was characterized by cleavage fracture. In order to clarify the SCC mechanism, the effects of inhibitor KI on SCC behaviour were also included in this paper. A study showed that the inhibition effects of KI on SCC were mainly attributed to the anodic reaction of the corrosion process. The results of strain distribution in front of the crack tip of the fatigue pre-cracked plate specimens in air, in the blank solution (acidic chloride solution without inhibitor KI) and in the solution added with KI measured by speckle interferometry (SPI) support the unified mechanism of SCC and corrosion fatigue cracking (CFC).

Comonomer sequence distribution in metallocene-based ethylene/1-butene (S-34) and ethylene/1-hexene (S-43) copolymers

Metallocene based polyethylenes were prepared by SMOPEC's "metallocene adduct" technology in a gas phase fluidized bed model reactor. The C-13-NMR spectra of ethylene/1-butene (S-34) and ethylene/1-hexene(S-43) copolymers were studied in a manner analogous to that established by Hsieh and Cheng. The comonomer sequence distributions of copolymer samples were obtained. The results show that these metallocene based copolymers contain a small amount of butene and hexene, and the EE and EEE sequences are dominant.