Tl-based superconducting films prepared by aerosol spray deposition and thallinated in an open system

Superconducting Tl-based films were prepared on a LaAlO₃ single crystal substrate. Spray pyrolysis of Ba, Ca and Cu nitrate solutions was used for deposition of the precursor films. They were subsequently ex-situ thallinated in flowing oxygen (open system). While the superconducting Tl-2212 phase formed at an annealing temperature of 880°C, thallination at 900°C led to the formation of a Tl-2223 /Tl-2212 mixture. The amount of Tl-2223 increased with prolonged thallination, whereas the Tl-2212 phase progressively disappeared. Films prepared in such a manner were c-oriented and contained only low amounts of non-superconducting impurities. The resulting samples were characterized by XRD and SEM and their T _C values were determined by resistive four-point measurements. They showed critical temperatures in the range of T _ON = 125–135 K, T _C0 = 91–93 K. Differences between the composition and properties of the obtained films and those thallinated in closed systems under 50 kPa of oxygen are discussed in this paper. Results show that the Tl-2212 → Tl-2223 transformation proceeds at a slower rate under flowing oxygen than in a closed system. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia.     

吡喃木糖热裂解机理的密度泛函理论研究

采用密度泛函理论理论方法M062X/6-311++G(d,p),对吡喃木糖的热解反应机理进行了理论计算分析。针对吡喃木糖热解可能发生的化学反应共设计了九条可能的热解路径,并对各路径中的反应物、中间体和过渡态的几何结构进行了能量梯度全优化,并在梯度全优化的基础上计算了各热解反应路径的热力学和动力学参数。文中以两大类方式来设计反应路径：1）木糖首先经过过渡态TS1发生开环反应生成链状中间体2,该步的反应能垒为188.7 kJ/mol,对于中间体2共设计了五种可能的热解反应路径;2）考虑双键同时断裂的情况,木糖先发生脱水反应,接着按C-C和C-O键同时断裂的情况发生开环反应,针于这种情况共设计了四条可能的热解路径。计算结果表明,吡喃木糖热解的主要反应产物有乙醇、乙醛、糠醛、丙酮、酸类、CO2和CO等小分子化合物。     

热重分析技术研究聚-α-甲基苯乙烯降解温度

采用热重分析技术研究了4种聚-α-甲基苯乙烯原料和其它微球壳层材料的热降解温度。研究表明,聚-α-甲基苯乙烯原料主要失重温度范围为220～340℃,等离子体辉光放电涂层材料的降解温度为350～450℃。升温速率在20℃/min和30℃/min时,降解温度基本相同,升温速率不影响降解的温度范围,低于20℃/min时,随着升温速率升高,降解温度升高。     

热分解法制备Bi替石榴石磁光薄膜的静态热磁模拟近似计算

对磁光薄膜进行热磁模拟可以了解影响热磁记录过程的各种因素及这些因素间的相互关系以及它们对写入信息的影响。采用近似计算方法对Bi、Al替DyIG磁光薄膜进行静态热磁模拟,得出在居里点写入的情况下写入点半径与定入功率、数值孔径、材料的反射率、材料的热导率及激光波长的关系。该方法为热磁定入过程提供了一种简捷的理论指导。     

Material Discrimination in Nanoparticle Hetero-Aggregates by Analysis of Scanning Transmission Electron Microscopy Images

Hetero-contacts are interfaces between different materials at the nanoscale leading to novel functional properties. In hetero-aggregates, primary particles of at least two different materials are mixed at primary particle or cluster level. Double flame spray pyrolysis (DFSP) is a versatile technique for the controlled synthesis of such materials. Characterization of hetero-aggregates by scanning transmission electron microscopy (STEM) requires acquisition and evaluation of many aggregate images in order to derive statistically significant results. Usually, STEM energy dispersive X-ray spectroscopy (EDXS) is used to acquire elemental maps providing the material distribution of the primary particles within hetero-aggregates. However, the acquisition of a single EDXS map takes up to several minutes. For this reason, determination of material types of primary particles from the intensity in high-angle annular dark field STEM images alone is desirable. These images can be acquired within a couple of seconds. In the present work, a method is suggested which allows for achieving this objective. It can be applied to distinguish materials with a significant difference in their atomic number and hence sufficient material contrast in the STEM images.     

中孔分子筛SO42-/Zr-MCM-41催化裂解聚丙烯反应研究

采用水热合成法制备了不同硅锆比的中孔分子筛Zr-MCM-41,用强酸性基团SO42-对其进行修饰,制得SO42-/Zr-MCM-41中孔分子筛.采用XRD、FT-IR、NH3-TPD及氮气吸附脱附等技术对其结构和酸强度进行表征.通过改变硅锆比、负载不同的酸性基团对Zr-MCM-41的酸性进行调变,并将其用于催化聚丙烯(PP)的裂解反应,结果表明S i/Zr=40的SO42-/Zr-MCM-41具有较好的催化裂解活性.另外,与热裂解以及HZSM-5和Zr-MCM-41为催化剂时PP的裂解反应结果进行了比较,结果证明SO42-/Zr-MCM-41不仅具有较高的裂解转化率,而且具有较高的液体产物收率,适宜于空间位阻较大的PP的催化裂解反应.     

裂解气相色谱-质谱法研究壬酸香草酰胺的热裂解

采用在线热裂解/气相色谱-质谱联用技术(Py/GC-MS)对壬酸香草酰胺(PAVA)的热裂解行为进行了研究,在氦气氛围中考察了不同裂解温度和裂解时间对PAVA裂解的影响,通过GC-MS对裂解产物进行定性和半定量分析。结果表明,随着裂解温度的升高,PAVA裂解率快速提高,裂解产物也进一步增多,当裂解温度达到700℃以上时,可裂解出壬酰胺、2-甲氧基-4-甲基苯酚、1-己烯、壬基腈、壬醛等14种产物。同一温度下随着裂解时间的延长,PAVA的裂解率逐步升高,裂解产物发生了进一步的裂解。根据热裂解产物及主要裂解产物的含量变化,初步推断了PAVA的裂解规律。     

Bi-2223喷雾热分解粉末热处理工艺优化

Bi-2223带材目前在电流引线、超导电机、超导电缆、超导限流器等领域实现了许多示范性应用,载流性能是表征其性能的重要指标,而高质量的前驱体粉末是最终带材性能的关键保障.本文选用具有工艺简单、粉末效率高、批次稳定性好等优点的喷雾热分解法制备的Bi-2223前驱体粉末,利用TG-DSC、XRD、SEM等测试手段对低氧条件下不同保温时间烧结的粉末进行分析,并结合最终带材的载流性能测试结果,获得了最优粉末烧结参数,为后续喷雾热分解粉末的进一步生成Bi-2223相以及高性能粉末的制备提供了依据.     

酸洗脱矿对胜利褐煤热解过程中N迁移转化的影响

在石英管流化床反应器中对胜利褐煤进行快速热解实验,考察了773~1 173 K下酸洗脱矿对胜利褐煤热解过程中N迁移转化规律的影响。通过比较原煤和酸洗后煤中N的不同逸出规律可以得出,影响酸洗前后胜利褐煤热解过程中N迁移转化规律的主要是碱金属Na及碱土金属Ca;热解过程中,煤中的Na和Ca促使煤中的N向NH3转化并有效抑制了HCN的生成,金属离子的存在对催化焦油N转化为NH3的作用较为明显;原煤中的碱金属和碱土金属的赋存使半焦裂解反应加剧,降低了固体半焦的产率,半焦N的产率也随之减少;与原煤相比,酸洗煤热解半焦中的吡啶型N(N-6)含量较多,而吡咯型N(N-5)和季N(N-Q)相对较少。