Graphite Oxide and Aromatic Amines: Size Matters

Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”.     

The assessment of commercial beef and chicken bouillons in terms of heterocyclic aromatic amines and some of their precursors

Herein, the assessment of commercial beef and chicken bouillons in terms of heterocyclic aromatic amines (HAAs) and some of their precursors was evaluated. Creatine and creatinine levels were ranged between 0.57–0.80 and 0.28–0.94 mg g⁻¹, respectively. Glutamic acid was found to be the most abundant amino acid in both bouillons. 2-amino-3,7,8-trimethylimidazo[4,5-ƒ]quinoxaline (7,8-DiMeIQx, up to 0.03 ng g⁻¹) was the only quantified analyte in beef bouillons, whereas it (up to 0.08 ng g⁻¹) was determined in addition to 2-amino-3-methylimidazo[4,5-ƒ]quinoxaline (IQx, up to 0.08 ng g⁻¹) in chicken bouillons. Creatine, creatinine and free amino acid composition did not have the capacity to initiate the formation of HAAs. Therefore, bouillons do not pose risk in terms of HAAs. However, it should be noted that multiple factors, such as the substrate amount and production conditions, may affect the results. Glutamic acid content is remarkable in commercial bouillons sold in Turkey.     

高效液相色谱法测定多环芳烃的出峰顺序探讨

目的探讨水﹑气﹑土壤中多环芳烃检测标准(HJ 478-2009﹑HJ 647-2013、HJ 784-2016)的正确出峰时间和顺序。方法用高效液相色谱来对苊烯、芴、苊、?、苯并(a)蒽进行定性分析,并与3个标准中的出峰顺序进行比较。结果苊烯、苊、芴、苯并(a)蒽、?的出峰时间分别为6.450、7.923、8.233、17.760、18.740min,与标准HJ478-2009﹑HJ647-2013的出峰顺序存在差异。结论在使用标准HJ478-2009﹑HJ647-2013、HJ 784-2016同时测定16种多环芳烃时,多环芳烃的出峰顺序及时间应以HJ 784-2016为准。     

Mechanism of smoke suppression by melamine in rigid polyurethane foam

The smoke suppression of rigid polyurethane foam (RPUF) modified by melamine was investigated based on three sections: the condensed phase, the carbon layer, and the gas phase. In the condensed phase, the results of thermogravimetry, X‐ray photoelectron spectroscopy (XPS) N1S spectrum, and Fourier transform infrared spectroscopy indicated that melamine could suppress the degradation of RPUF by reacting with the aromatic hydrocarbons. It also reduced the smoke generation because the volatilizable aromatic hydrocarbons were the principal smoke precursors in a fire. In the carbon layer, the decrease from 38.50% to 24.76% of the inner layer oxygen content identified by XPS full‐spectrum and C1S spectrum indicated that melamine could prevent oxygen from transferring into the inner foam by the formation of an enhanced surface carbon layer, and the enhanced carbon layer could also block the release of smoke precursors. In the gas phase, the content of total aromatic hydrocarbons declined to 59.12% according to pyrolysis gaseous chromatography mass spectroscopy and indicated that melamine could reduce the smoke precursors. The results of smoke density chamber and cone calorimeter tests revealed that the addition of the melamine could decrease the smoke density of burning RPUF. Copyright © 2014 John Wiley & Sons, Ltd.     

High-Tg porous polyimide films with low dielectric constant derived from spiro-(adamantane-2,9′(2′,7′-diamino)-fluorene)

Porous polyimide (PI) films with low dielectric constants and excellent thermal properties have been a pressing demand for the next generation of high-performance, miniature, and ultrathin microelectronic devices. A series of novel porous PI films containing fluorenyl-adamantane groups were prepared successfully via thermolysis of poly(ethylene glycol) (PEG) added in the PI matrix. The cross-sectional morphologies of porous PI films showed closed pores with diameters ranging from 135 to 158 nm, which were uniform and regular in shape without interconnectivity. These porous PI films exhibited excellent thermal properties with a glass-transition temperature at 376 °C whereas the 5% weight loss temperature in air excess of 405 °C due to enhanced rigidity afforded by fluorenyl-adamantane groups. Accompanied by thermolysis content of PEG increasing from 0 to 20 wt %, the density of porous PI films decreased, and the corresponding porosity grew significantly from 0 to 11.48%. Depending on porosity, the dielectric constant and dielectric loss of porous PI films significantly declined from 2.89 to 2.37 and from 0.050 to 0.021, respectively. These excellent properties benefit the as-prepared porous PI films for application as interlayer dielectrics, integrated circuit chips, or multichip modules in microelectronic fields. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47313.     

芳烃联合装置节能降耗方法探讨

结合芳烃联合装置的发展形势，通过对国内某4套典型芳烃联合装置运行能耗的构成进行分析，确定该类装置的主要能耗在于燃料、电和蒸汽的消耗。总结了目前国内外常用的芳烃联合装置节能降耗方法，利用实际经验和调研结果，从采用新型吸附剂、采用单台吸附塔新工艺、采用轻质解吸剂替代对二乙苯（PDEB）、优化吸附塔运行参数、加热炉节能优化和选用高效节能设备等角度探讨芳烃联合装置的节能降耗方法。芳烃联合装置节能降耗应该由设计单位和生产单位紧密结合，在设计阶段就应充分考虑生产过程面临的问题，充分优化工艺路线、方案和设备设计，尽可能降低装置的能耗。同样，装置运行过程中，生产部门应标准化、精细化管理，优化日常操作，从而进一步降低装置的操作能耗。     

岩石圈深部温度压力条件下褐煤与水的热模拟研究

在压力高达1—3GPa、温度为400—700℃的条件下，在密闭体系中进行了褐煤加水的模拟实验。分析了实验产物中液态烃的变化规律，并讨论了压力、温度及恒温时间对有机质演化的影响。实验结果表明，热模拟液态产物氯仿沥青“A”的有机碳含量为0．91％-2．55％，2GPa条件下其高峰值后移至700℃，说明高压抑制了液态烃的生成，同时压力升高有利于有机质降解产物的环化、聚合和芳构化。在400—600℃条件下，温度升高或恒温时间增长，OEP和Pr／Ph值均减小；而在700℃的恒温条件下，压力增高，OEP和Pr／Ph值均增大。说明有机质的成熟度与温度和加热时间成正相关，而压力增加抑制了有机质的成熟演化。在高压条件下，芳烃演化的主要趋势是甲基化作用，压力升高有利于甲基化反应和甲基重排。     

含氮化合物对NiW体系催化剂芳烃加氢性能的影响

以γ-Al2O3、B改性的γ-Al2O3、F改性的γ-Al2O3、SiO2-Al2O3为载体制备Ni、W含量相同的四种催化剂，通过程序升温还原表征考察活性金属与不同载体的相互作用。利用氮含量不同、四氢萘含量相同的四种原料考察含氮化合物对同种NiW体系催化剂四氢萘加氢的影响以及对活性金属与载体相互作用不同的催化剂四氢萘加氢的影响。结果表明，以γ-Al2O3或SiO2-Al2O3载体制备的催化剂的金属组分与载体相互作用较强，B或F改性的γ-Al2O3能显著削弱活性金属与载体的相互作用；含氮化合物对四氢萘加氢具有强烈的抑制作用，使四氢萘加氢反应的表观活化能增加；在实验研究的四种催化剂中，金属组分与载体相互作用较弱的催化剂受含氮化合物的抑制较强。