Acceleration of the cationic polymerization of an epoxy with hexanediol

Thin films of 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate were UV irradiated (1.1 J cm^-2) under isothermal conditions ranging from 0 to 50°C. Under these conditions the polymerization advanced quickly but only to a conversion level of less than 10% before the reaction rate slowed by more than an order of magnitude. This drop off in rate was not caused by the glass transition temperature, T _g, reaching or exceeding the reaction temperature, T _rxn, since the epoxide's T _g remained at least 40°C below T _rxn. Raising the sample temperature above 60°C caused a sharp increase in the conversion level. At 100°C conversion exceeds 80% and the ultimate T _g approaches 190°C. The addition of 10 mass% 1,6-hexanediol, HD, to the epoxy caused the conversion at room temperature to quintuple over the level obtained without the alcohol present. The heat liberated from this alcohol epoxy blend during cure on a UV conveyor belt system caused the sample's temperature to increase by about 100°C above ambient whereas the epoxy alone under these conditions only experienced a modest temperature rise of about 26°C. If the amount of HD in the blend is increased above 10% the heat of reaction at 23°C decreases due to HD being trapped in a nonreactive crystalline phase. Boosting reaction temperatures above 50°C melts the HD crystals and yields significantly improved conversion ratios. As the level of alcohol blended with the epoxy is raised its ultimate T _g is lowered and when the concentration of alcohol in the blend nears 30 mass%T _g drops below room temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

High temperature NMR approach of mixtures of rare earth and alkali fluorides: An insight into the local structure

In situ high temperature nuclear magnetic resonance in molten fluoride mixtures gives some structural picture of the complexes existing in the melt, i.e. of their nature and relative proportion. Thanks to the development of a laser heating system associated with a close crucible in boron nitride, we can describe experimentally the evolution of these complexes from the anions and the cations point of view. By ¹⁹F NMR, we have shown the existence of three kinds of fluorine atoms depending on the composition: free fluorine like in pure LiF (non-bonded), bridging fluorine in melts rich in LnF₃ in addition with terminal fluorine singly bonded to one rare earth. Data obtained by NMR spectroscopy are also combined with EXAFS measurements, again thanks to a specific development of the sample holder adapted with molten fluorides and high temperature. This study is a part of our systematic investigation of the different Alk-LnF₃ systems by NMR and EXAFS spectroscopy.     

焙烧及还原温度对 Co-Pt-ZrO2/γ-Al2O3催化剂费托合成反应性能的影响

采用浸渍法制备了Co-Pt-ZrO₂/γ-Al₂O₃催化剂,对其进行了BET、XRD和TPR等表征,并在浆态床反应器上考察了焙烧温度和还原温度对催化剂费托合成反应性能的影响。结果表明,焙烧温度过高,容易造成Co物种和载体间的相互作用增强,使部分氧化钴颗粒聚集或烧结,导致催化剂的F-T合成反应活性和C₅₊烃选择性降低。还原温度较低时,钴物种不能充分还原,CO加氢活性低,甲烷选择性高,重质烃选择性低;还原温度过高,则可能造成活性物种的烧结,反而降低了催化剂的活性和重质烃选择性。在原料气n(H₂)/n(CO)=2.0、483 K、2.4 MPa和空速3.6 L/(gcat·h)的条件下,31.08%Co～0.11%Pt～7.16%ZrO₂/Al₂O₃催化剂在673 K焙烧。纯H₂下653 K还原后,其费托性能最佳;CO转化率为27.0%,C₅₊的选择性为83.0%。     

Co3O4/CeO2的氧化还原性能及反应条件对其CO氧化活性的影响

采用沉淀氧化法制备了Co₃O₄/CeO₂催化剂。运用XRD、BET和TPR表征手段,考察了不同钴铈比及焙烧温度对钴铈复合氧化物物理及化学性能的影响,并分别在干、湿条件下进行了一氧化碳氧化反应研究。结果表明,与纯的Co₃O₄相比,在不同比例的Co₃O₄/CeO₂均经723 K焙烧的各种催化剂中,钴铈原子比为9∶1的复合氧化物粒径较小,比表面积较大,说明适当比例铈的添加能使Co₃O₄具有较小的粒径。此氧化物经538 K温度焙烧制得的钴铈比为9∶1的复合氧化物中Co₃O₄平均粒径为7.2 nm, BET比表面积为167.6 m²/g。经TPR考察发现其具有最优的氧化还原性能。     

还原温度对Fe-Mo催化剂性质及F-T合成性能的影响

研究了还原温度对Fe-Mo催化剂性质及费托(F-T)合成性能的影响。采用N₂物理吸附、X射线衍射、穆斯堡尔谱和H₂程序升温脱附技术对催化剂进行了表征。结果表明,随还原温度升高,金属铁晶粒粒径增大,金属铁上的H₂吸附量先升后降;催化剂还原度提高,反应态催化剂碳化铁含量递增。催化剂F-T合成性能在280 ℃、1.5 MPa、2 000 h^-1、合成气H₂/CO比为2.0条件下在固定床反应器中测试。反应结果表明,随还原温度提高,催化剂接近稳态时的活性和重质烃选择性(C₅⁺)先升后降,而甲烷选择性则先降后升。350 ℃还原催化剂具有最佳F-T合成反应性能。     

菱镁矿风化石与叶腊石合成堇青石的结构表征

采用菱镁矿风化石、叶腊石、二氧化硅微粉为主要原料,研究分析烧成温度对合成堇青石结晶度、晶粒尺寸、晶相组成和显微结构来确定适宜的合成温度。用X′ Pert plus软件对X射线衍射图进行拟合,分析试样的结晶度,用半定量(semi-quantification)法对试样结晶相中晶相组成进行计算,用Scherrer公式计算试样中堇青石、方石英晶粒的粒径大小。结果表明：采用菱镁矿风化石与叶腊石为原料合成堇青石,当温度由1 350 ℃增加到1 400 ℃,试样的结晶度增加,堇青石晶粒尺寸和堇青石相量增加,在1 400 ℃时,试样结晶度最高,晶粒尺寸最大。晶相组成中堇青石相占67%,方石英相占33%。当温度大于1 400 ℃,试样结晶度降低,堇青石和方石英晶粒尺寸减小,当温度在1 500 ℃时,堇青石相消失,促进了方石英相析出。采用菱镁矿风化石与叶腊石为原料合成堇青石的最佳烧成温度为1 400 ℃。     

二(三氟甲基磺酰)亚胺锂对磷酸铁锂正极高温行为的影响

系统研究了电解质锂盐对磷酸铁锂电极高温性能的影响, 并探讨了相关的作用机理. 差示扫描量热仪测试显示, 与LiPF₆相比, 二(三氟甲基磺酰)亚胺锂(LiTFSI)和LiBF₄具有对水份稳定且热稳定性好的优点, 更适合高温条件下使用. 应用等离子体发射光谱考察LiFePO₄在55 ℃和不同电解液体系中铁离子溶出程度, 结果表明, 在LiTFSI和无氟锂盐电解液中LiFePO₄的铁很少溶出, 而在LiPF₆电解液中却溶出严重, 且FePO₄的铁溶出量高于LiFePO₄. 循环伏安和光学显微镜测试结果显示少量LiBF₄的加入能有效抑制LiTFSI对集流体铝箔的腐蚀. 以LiTFSI和LiBF₄作为混合锂盐配成的电解液能显著改善LiFePO₄/Li电池的高温电化学性能, 在55 ℃和1 C倍率下循环40次后放电比容量达147.7 mAh/g.     

几种纤锌矿相半金属铁磁体磁学性能的第一原理研究

通过基于密度泛函理论的第一原理计算,优化了纤锌矿结构的化合物TmZn15S16(Tm=V,Cr,Mn)的几何结构,并研究了它们的磁学性能.结果表明:TmZn15S16均为典型的半金属铁磁体,它们的超胞磁矩分别为3.0099μB,3.9977μB和5.0092μB;这些磁矩主要来源于被掺入的过渡元素;CrZn15S16的半金属特性比VZn15S16和MnZn15S16更稳定;这些半金属铁磁体的半金属带隙均比较宽,表明它们可能具有较高的居里温度;TmZn15S16中杂质过渡离子的电子结构分别为V:eg2↑t12g↑,Cr:eg2↑t22g↑和Mn:eg2↑t32g↑.     

用于NH3选择性催化还原NO的非钒基催化剂研究进展

NH3选择性催化还原NO (NH3-SCR)技术在燃煤电厂烟气脱硝过程中有着多年的工业应用经验,也是最有望实际应用于柴油车尾气NOx催化去除的技术之一.鉴于目前工业化应用的V2O5-WO3 (MoO3)/TiO2催化剂体系应用于柴油车尾气净化仍存在着诸多问题,开发新型、高效、稳定且环境友好的非钒基NH3-SCR催化剂体...     

高压变质二氧化硅矿物的合成及表征

根据高能机械球磨与地球板块碰撞之间具有的碰撞局域性和剪切应力相似的特点, 采用高能机械球磨和静高温高压技术, 以α-石英与石墨混合粉末为原料, 提出了人工合成地表柯石英的一种新方法. 利用高能机械球磨制备了α-石英和石墨纳米非晶混合粉末, 其高温高压合成柯石英的最低条件是970 K和3.7 GPa. 合成的柯石英有10个Raman峰, 分别位于120, 152, 179, 206, 270, 329, 357, 428, 467和521 cm-1, 是目前最全的柯石英Raman谱.