Controlling the Deintercalation in Hydrogenated Nitrile Rubber (HNBR)/Organo‐Montmorillonite Nanocomposites by Curing with Peroxide

Summary: The effect of peroxide vulcanization on organoclay dispersion in hydrogenated nitrile rubber (HNBR)/organo‐montmorillonite (organo‐MMT) nanocomposites was investigated. Three types of organoclays were tested, one containing a primary amine and two bearing quaternary intercalants. In contrast to sulfur vulcanization, which in combination with primary amine intercalants produced a confined/deintercalated clay structure, the peroxide curing yielded well‐ordered intercalated nanocomposites. The tensile mechanical performance and oxygen permeability of the HNBR nanocomposites were determined.

Oxygen permeability coefficient ratio for the different HNBR films tested at 0 and 60% relative humidity (i.e., dry and wet conditions, respectively).     

原位聚合甲基丙烯酸盐/低温氢化丁腈橡胶的结构与性能

采用不同阳离子的碱和甲基丙烯酸(MAA),通过混炼和硫化过程的原位聚合,制备了聚甲基丙烯酸盐(SPMAA)改性氢化丁腈橡胶(SPMAA-HNBR).用扫描电子显微镜、透射电子显微镜、傅里叶变换红外光谱仪、示差扫描量热仪及浸泡溶胀实验研究了SPMAA阳离子种类(Na+,Mg2+和Al3+)对SPMAA-HNBR性能的影响.结果表明,随着阳离子电荷数的增加,SPMAA逐渐在SPMAA-HNBR内部形成强的离子簇结构,导致其与HNBR间的相容性变差,甚至出现大尺寸的聚集体.这种明显的相分离结构造成聚甲基丙烯酸铝(Al SPMAA)改性氢化丁腈橡胶的拉伸强度和耐油溶胀性能都低于含电荷数较少的聚甲基丙烯酸钠(Na SPMAA)和聚甲基丙烯酸镁(Mg SPMAA)改性氢化丁腈橡胶的性能.各种SPMAA-HNBR的玻璃化转变温度均未发生变化,保持了-30℃的低温弹性.因此,选择生成不同阳离子的SPMAA,可在保持HNBR低温性能的基础上,有效控制SPMAA-HNBR的性能.     

脱除低浓度硫化氢的改性活性炭纤维的再生研究

用改性的活性炭纤维（ACF）脱除低浓度的H2S是一种十分有效的方法,但脱硫后的改性ACF容易达到脱硫饱和而失活。用溶剂再生和气体热再生的方法可以对失活后的改性ACF进行再生。在固定床反应器上考察了再生后ACF的脱硫性能。实验结果表明,与溶剂再生相比,气体热再生是更有效的再生方法。不同再生方法的效果的不同,是由ACF脱除H2S的反应机理的不同和再生机理的不同造成的。     

活性炭纤维吸附脱除硫化氢研究进展

从活性炭纤维(ACF)的结构特点、未改性ACF吸附H2S和改性ACF吸附H2S三方面综述了国内外对ACF吸附H2S的研究进展。归纳了ACF的改性方法、ACF吸附H2S的反应机理和动力学研究。总结了相对湿度、原料气组成、生成物和改性方法等工艺条件对ACF吸附H2S性能的影响。展望了改性ACF吸附脱除H2S的研究前景。     

低温等离子体处理化工恶臭污染物硫化氢的研究

采用电晕放电低温等离子体处理模拟硫化氢恶臭气体,考察了输入功率、初始浓度、气体湿度、停留时间等因素对降解效果和能量效率的影响,同时对反应过程进行了动力学研究。研究表明：输入功率以及停留时间对硫化氢降解的影响是积极的,但能量效率随着两者的增加先增大后减小。硫化氢的降解率随着初始浓度的增加而降低,而能量效率随着初始浓度的增加而增加。在气体湿度增加初期,硫化氢降解率和能量效率均随着气体湿度的增加而增加,当气体湿度为50%时达到最大值,然而随着气体湿度的进一步增加,其降解率和能量效率反而降低。对电晕放电低温等离子体处理硫化氢的反应动力学进行了分析,得到硫化氢的反应速率常数为kH2S=0.356 8 m3/（W·h）。     

DMA水溶液的1H NMR研究

测量了N，N-二甲基乙酰胺(DMA)水溶液体系不同温度下全浓度范围的^1H NMR数据，对体系中的缔合情况进行了讨论。应用化学缔合模型求得了各缔合平衡常数K和缔合平衡的△H，结合N，N-二甲基甲酰胺(DMF)和N-甲基乙酰胺(NMA)水溶液的研究结果，发现酰胺自身结构和酰胺浓度是影响酰胺水溶液性质的主要因素。     

无氧条件下Pt/TiO_2光催化重整降解—乙醇胺水溶液制氢

以-乙醇胺(以下简称乙醇胺)为电子给体,在无氧条件下进行了Pt/TiO2光催化重整制氢的研究.详细讨论了诸多因素如催化剂表面Pt化学状态、Pt担载量、溶液pH值、乙醇胺溶液浓度等对产氢效率的影响,并用XRD、HNMR、XPS等进行了深入表征,探讨了Pt/TiO2光催化重整降解乙醇胺和产氢的反应,实验表明,利用所制备的光催化剂,可实现在消除水中有机污染物的同时制取氢气的目标.催化剂表面的Pt以Pt0的化学状态存在,有利于析氢;溶液pH值和浓度的变化对产生速率也有一定的影响.同时发现Pt/TiO2光催化重整乙醇胺制氢反应的最佳条件是:Pt的最佳担载量约为0.5％-1.0％;乙醇胺溶液最佳浓度约为0.05 mol·L-1;最佳溶液pH值范围为4-10;氨基取代的羰基类化合物是其主要中间产物.     

DFT studies on the mechanism of the reaction of C2H5S with NO2

The mechanisms for the reaction of C₂H₅S with NO₂ are investigated at the QCISD(T)/6‐311++G(d, p)//B3LYP/6‐311++G(d, p) level on both single and triple potential energy surfaces. The geometries, vibrational frequencies and zero‐point energy (ZPE) corrections of all stationary points involved in the title reaction are calculated at the B3LYP/6‐311++G(d, p) level. The results show that the reaction is more predominant on the single potential energy surface, while it is negligible on the triple potential energy surface. Without barrier height in the whole process, the major channel is R → C₂H₅SONO (IM1 and IM2) → P1 (C₂H₅SO+NO). With much heat released in the formation of C₂H₅SNO₂ (IM3) and the transition state involved in the subsequent step more stable than reactants, P4 (CH₃CHS + t‐HONO) is subdominant product energetically. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Anti‐corrosion properties of bis(benzimidazole) derivatives for N80 steel in H2S solution

In this work, we systematically investigated the effect of four bis(benzimidazole) derivatives containing different heteroatoms in molecular structures on inhibiting corrosion of N80 steel in 0.5 mmol·l^?1 H₂S solution by potentiodynamic polarization, electrochemical impedance spectroscopy and metallographic microscope. The results showed that within the range of 0.1–1.0 mmol·l^?1, the adsorption of bis(benzimidazole) derivatives on N80 steel surface was found to follow Langmuir adsorption isotherm. Meanwhile, stable adsorbing monolayer between inhibitors and the metal surface was formed, which was confirmed by thermodynamic adsorption parameters (K_ads, ). This series of bis(benzimidazole) derivatives exhibited obvious corrosion inhibitory properties for N80 steel. Moreover, they could both slow down the anodic dissolution of iron and the cathodic reduction reaction as mixed type corrosion inhibitors. The optimal inhibition efficiency was obtained for 1,3‐bis(benzimidazl‐2‐yl)‐2‐thiapropane (BBMS). Hopefully, this series of inhibitors might find applications in anti‐corrosion and many other areas. Copyright © 2012 John Wiley & Sons, Ltd.     

离子液体和醇胺溶液复配脱硫剂吸收H2S及再生性能

将5种离子液体[Bmim]HCO₃, [TMG]L, [MEA]L, [Bmim]Cl和[Bmim]BF₄分别与N-甲基二乙醇胺(MDEA)水溶液混合, 得到新型复配脱硫剂, 考察了离子液体的消泡性能和复配脱硫剂在不同离子液体、 吸收温度以及复配比例下的脱硫性能, 并且对较优脱硫剂进行了再生性能的研究. 采用离子色谱仪对经臭氧深度处理的再生液进行了S\begin{array}{c}{O}_4^{2-}\end{array}离子浓度测试, 并对脱硫剂进行了密度泛函理论研究, 从而进一步分析了吸收机理. 结果表明, 室温下复配脱硫剂脱硫能力大小顺序为[Bmim]Cl-MDEA-H₂O>[Bmim]HCO₃-MDEA-H₂O>[Bmim]BF₄-MDEA-H₂O>MDEA-H₂O>[TMG]L-MDEA-H₂O>[MEA]L-MDEA-H₂O. 离子液体与MDEA结合的稳定性为主要影响因素, [Bmim]HCO₃的消泡能力最强, [Bmim]Cl-MDEA-H₂O, [Bmim]BF₄-MDEA-H₂O和[Bmim]HCO₃-MDEA-H₂O脱硫剂可以通入空气获得基本再生, H₂S与离子液体的结合越稳定, 脱硫效率越高, 但脱硫剂的再生程度会降低.     

Potential energy surfaces for van der waals complexes of rare gases with H2S and H2S2: Extension to xenon interactions and hyperspherical harmonics representation

This article is an account and extension of a series of recent investigations, which using extensive quantum chemical methods provide analytical hyperspherical representations of the potential energy surfaces for the interactions of rare gases with H₂S as a rigid molecule, and H₂S₂, considered as a floppy molecule with respect to torsional mode. For the H₂S‐rare gas systems, the representation is based on a minimal model, here introduced and discussed. For H₂S₂, the study of the interaction with Xe, not considered previously, completes the series. The results are discussed with reference to the properties and trends expected for interactions of van der Waals type. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Sensitive Electrochemical Detection of Pb(II) and H2O2 via a Dual-functional Sn-doped Defective Bi2S3 Microspheres

In this work, a dual-functional electrochemical sensor has been proposed based on Sn-doped defective Bi₂S₃ (TDDB) microspheres, which exhibited the excellent electrochemical performance on Pb(II) and H₂O₂ detection. The TDDB offered a satisfied detection limit of 8.0 nM towards Pb(II) with a sensitivity of 96.7 μA ⋅ μM⁻¹. As a H₂O₂ sensor, a high sensitivity of 3540 μA mM⁻¹ cm⁻² was obtained in a linear range from 0.45 mM to 10 mM with a detection limit of 10 nM. Moreover, the electrochemical detection of Pb(II) in Taihu Lake and H₂O₂ in human serum was achieved with high reliability and good recovery.     

Network characteristics of hydrogenated nitrile butadiene rubber networks obtained by radiation crosslinking by electron beam

The effects of high-energy radiation on hydrogenated nitrile butadiene rubber (HNBR) copolymer structure and properties were studied. Characterization by FTIR spectroscopy, swelling and mechanical measurements of irradiated and un-irradiated sample permit us to correlate the change in structure with properties. The modifications obtained are dependent on the radiation dose of the incident electron beam. FTIR spectroscopy in absorption mode shows that irradiation of HNBR first induces trans-vinylene bond formation and secondly small amounts of carbonyl (CO) groups. Moreover, more significant changes were observed with swelling method and mechanical behaviour showing the effect of crosslinking on the elastomer.     

单个水分子对HO2+H2S反应主通道影响的理论研究

采用CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p)方法对HO2+H2S反应及单分子水参与其主通道的微观机理和速率常数进行了研究.结果表明,HO2+H2S反应主通道为生成产物为H2O2+HS的通道,其表观活化能为14.94 kJ/mol.考虑单分子水对主产物通道的影响发现,所得的势能面比无水参与的反应复杂得多,经历了H2O…HO2+H2S(RW1),HO2…H2O+H2S(RW2)和H2O…H2S+HO2(RW3)3个通道,RW1~RW6共6个路径.其中通道RW1是水分子参与HO2+H2S反应主通道的优势通道.在216.7~298.2K温度范围内通道RW1的有效速率常数呈现出正温度系数效应,在298 K时,k’RW 1/ktotal达到54.2%,表明在实际大气环境中水分子对HO2+H2S反应的主通道具有明显影响.     

咪唑啉衍生物在H_2S水溶液中的腐蚀抑制机理(英文)

使用失重法和电化学极化技术研究了咪唑啉衍生物在H2S水溶液中对碳钢腐蚀的抑制机理.结果表明:咪唑啉衍生物能有效抑制H2S的腐蚀,属于阴极型缓蚀剂.咪唑啉衍生物在金属表面上的吸附符合Langmuir等温吸附,温度越高,越有利于吸附.加入缓蚀剂后,降低了腐蚀反应的活化能和指前因子,而指前因子是腐蚀反应的决定因素,因此缓蚀剂的加入能降低腐蚀速率.     

Study on ablative properties and mechanisms of hydrogenated nitrile butadiene rubber (HNBR) composites containing different fillers

The ablative properties of hydrogenated nitrile butadiene rubber (HNBR) composites filled with fumed silica, organically modified montmorillonite (OMMT), or expanded graphite (EG) were examined. The HNBR/OMMT composite has the lowest linear ablation rate and the highest mass ablation rate and does not tend to be carbonized. On the other hand, the HNBR/EG composite has the highest linear ablation rate and the lowest mass ablation rate, and is prone to carbonization. The ablative properties of the HNBR/silica composite are between those of HNBR/OMMT and HNBR/EG. From the viewpoint of thermal shielding capability, the HNBR/OMMT has the best ablation resistance. Thermogravimetric analysis (TGA) on different HNBR composites indicated that the filler type has no significant effect on the thermal stability of the composites. To understand the ablation mechanisms, the char layers of different HNBR composites after ablation experiments were characterized by scanning electron microscopy (SEM), energy disperse X-ray spectroscopy (EDS), and wide-angle X-ray diffraction (WAXD). The results showed that the porosity in the char layers of the HNBR/OMMT composite was the highest and the corresponding structure was the loosest of the three composites. The montmorillonite (MMT) dispersed in HNBR experienced phase transition, melting and vaporization when exposed to the flame with the temperature over 2000 °C. Fumed silica only melted at such situation. On the other hand, the EG kept their original crystalline structures after the ablation test. Based on these results, the effect of the filler type on the ablation mechanisms of the HNBR composites was discussed.     

含二茂铁基荧光探针对H2S的识别

以乙酰二茂铁和蒽醛为原料,合成了一种新的反应型荧光探针1-二茂铁基-3-(9-蒽基)丙烯酮,经1H NM R,13C NM R,IR,LC-M S等手段表征确证。基于Michael加成引起的电子转移机制,利用硫化氢的强亲核性,以荧光滴定法考察了该化合物在生理条件下对硫化氢的识别作用,得出其最佳识别时间为50 min,最佳识别浓度为50μmol/L,且多数离子不会对其识别作用产生干扰。这种能稳定检测的,具有高选择性、高灵敏度的反应型荧光探针化合物,可用于生物医药领域。     

TiO2光催化消除H2S的研究

在TiO₂上进行了气相H₂S光催化氧化消除的研究.氧对H₂S的光催化氧化消除过程是不可缺少的,对含量为560mg/m³的H₂S,当加入的氧气与原料气中H₂S的分子比为42:1,空速为28000h^-1时,去除率达到97%.在H₂S光催化氧化消除过程中,单质硫的产生可使TiO₂失活,经光照再生单质硫转化为SO₄^2-后,TiO₂活性恢复,而且SO₄^2-的生成对催化剂的中毒有抑制作用.     

高硫合成气制甲硫醇钼硫基催化剂的制备

钼硫基催化剂;含硫化氢合成气;高硫合成气制甲硫醇钼硫基催化剂的制备     

Pt/TiO2光催化重整降解2-氯乙醇水溶液制氢

在无氧条件下,进行了Pt担载的TiO2光催化有毒的2-氯乙醇(下文简称氯乙醇)重整制氢反应的研究.详细讨论了动力学因素如催化剂表面Pt化学状态、Pt担载量、溶液pH值、氯乙醇浓度等对产氢速率的影响,并用XRD、HNMR、XPS等技术进行了表征,探讨了氯乙醇降解和产氢反应机理.研究表明,在光催化降解氯乙醇的同时产生氢是完全可行的.催化剂表面的Pt以Pt0的化学状态存在,有利于析氧;溶液pH值对产生速率影响也很大,而氯乙醇的浓度变化只是在开始略有影响,浓度的增加对产氢并没有明显的影响.研究得出Pt担载的TiO2光催化重整氯乙醇制氢反应的最佳条件是Pt的最佳担载量约为1.0%;氯乙醇溶液浓度范围为0.04～0.10 M;最佳溶液pH值范围为4～10.