十六烷基三甲基溴化铵改性X分子筛对铬酸盐的吸附平衡及动力学

用十六烷基三甲基溴化铵(HTAB)对X分子筛改性,考察改性分子筛对水中铬酸盐的吸附平衡及吸附动力学。采用XRD和FT-IR对样品进行表征,结果表明改性后HTAB-X分子筛在保持原有结构和形貌同时,接枝了一定量的长链季铵盐阳离子功能基团。吸附实验表明,0.7 g改性分子筛在25℃、pH=6条件下,去除率为94.14%,比X分子筛提高了近36%。HTAB-X分子筛对铬酸盐的吸附遵循Langmuir模型,最大吸附容量为16.33 mg/g。热力学和动力学分析表明,该吸附过程为自发的放热过程,适合在常温下进行;吸附过程遵循准二级动力学模型,平衡吸附容量qe,cal达到2.71 mg/g,速率常数k2为0.362 g/(mg·min)。     

Clay distribution and crystalline structure evolution in polyamide 6/montmorillonite composites prepared by activated anionic polymerization

Nanostructured polymer composites (NPC) based on polyamide 6 (PA6) are prepared by activated anionic ring‐opening polymerization (AAROP) of mixtures of ε‐caprolactam (ECL) and organically treated montmorillonite (o‐MMT). The polymerization is performed in bulk, at 165°C, i.e., below the melting point of the resulting APA6, the reaction time being in the range of 10–15 min. The o‐MMT content is varied in the 0.5–10% range. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) show that exfoliated NPC can be produced with clay loads of 0.5–1.0%. Larger clay amounts lead to various degrees of intercalation of the MMT layers. FT‐IR imaging proves that all NPCs contain MMT aggregates with sizes in the 10–20 µm range. The formation of the matrix crystalline structure is followed directly by performing AAROP of an activated ECL/o‐MMT blend in a synchrotron beamline. Irrespective of the o‐MMT type and concentration, it is the α‐PA6 that forms first and in larger amounts. The γ‐PA6 polymorph can be found in predominating amounts only after melting and recrystallization of the already produced polymer matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1228‐1238, 2013     

用原位有机改性法制备的溴化丁基橡胶／蒙脱土复合材料的性能

采用原位有机改性法制备了溴化丁基橡胶(BIIR)/蒙脱土(MMT)复合材料,并对其硫化特性和力学性能进行了研究,用X射线衍射仪时复合材料中MMT的层间距进行了表征,并与钠基蒙脱土(Na-MMT)、有机蒙脱土(OMMT)和BIIR形成的复合材料进行了对比.结果表明,用原位有机改性法制备的BIIR/MMT复合材料的硫化特性和力学性能优于BIIR/Na/MMT复合材料,甚至优于BIIR/OMMT复合材料;采用原位有机改性法,可使BIIR/MMT体系中MMT的插层效果明显改善.     

不同工艺制备的PP/蒙脱土纳米复合材料的性能

选择一种新型有机蒙脱土（MMT）,分别通过直接注塑法和挤出一注射法（简称挤出法）将聚丙烯（PP）与有机MMT复合,制备出高抗冲PP／MMT纳米复合材料。透射电子显微镜观察表明。挤出法制备的复合材料为全插层型结构,MMT分散均匀,尺寸小;而直接注塑法制备的复合材料为部分插层型结构．MMT明显分散不均匀,尺寸较大,且有少量团聚产生。力学性能测试表明,随着MMT的增加．2种试样的缺口冲击强度都有显著提高,均在ω（MMT）为4％时达到极大值。此时,挤出法试样缺口冲击强度比纯PP提高102％。屈服拉伸强度、弹性模量也略有提高;直接注塑法试样的缺口冲击强度比纯PP提高82．6％,但屈服拉伸强度、弹性模量都明显降低。     

Flame retardancy of unsaturated polyester composites with modified ammonium polyphosphate,montmorillonite, and zinc borate

Ammonium polyphosphate (APP) was modified using a new method, where the resulting modified APP (MAPP) was obtained by mixing APP with unsaturated polyester resin (UPR). MAPP was more effective in improving the flame retardancy of UPR than APP which was due to the improved dispersion of MAPP in UPR composite. Then, the UPR composites were prepared based on dimethyl methylphosphonate, MAPP, montmorillonite, and zinc borate. Finally, the flame-retardant and mechanical properties of the UPR composites were analyzed using the limited oxygen index (LOI), thermogravimetric analysis, UL-94 vertical burning test, scanning electron microscopy, cone calorimetry, mechanical tests, and viscosity measurements. The LOI and UL-94 tests showed that the flame-retardant properties clearly improved with the addition of fillers in the UPR composites compared to pristine UPR. The synergistic effect of Si- and P-containing flame retardants in this composite resulted in the LOI value increasing from 18.9 to 31.3% and achieved the UL-94 V-0 rating. Moreover, the heat release rate was lower than the pristine UPR. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47180.     

FeCl3和十六烷基三甲基溴化铵改性赤泥对水中铜离子的吸附性能和机理

含铜废水主要来自电镀、有色冶炼、有色金属矿山开采、染料生产等过程。因Cu(Ⅱ)具有高毒性和生物富集性,严重威胁生态环境和人类健康。利用浓盐酸、三氯化铁（FeCl₃）、十六烷基三甲基溴化铵（CTAB）依次对拜耳法赤泥（RM）进行处理、改性,制备出了一种去除率高、吸附量大、吸附效果好的重金属离子吸附剂。通过SEM、TEM、XRD、BET、元素分析、FTIR、热重分析等手段对其进行表征,并探究溶液pH、吸附剂投加量以及吸附温度等条件对水溶液中Cu(Ⅱ)吸附效果的影响。结果表明：酸浸赤泥（RM-HCl）比表面积比RM增大20倍,经过FeCl₃和CTAB改性后赤泥表面负载了大量羟基氧化铁（FeOOH）并且改善了吸附材料的表面性质,提高了吸附材料与Cu(Ⅱ)之间的亲和力和单层吸附能力。综合改性赤泥（FeCl₃/CTAB/RM）对铜的吸附时间在100min达到平衡,其最佳吸附pH为6、最佳吸附剂投加量为2g/L、饱和吸附量为221mg/g。吸附过程较好地符合准二级动力学模型和Langmuir吸附等温模型,热力学数据说明该吸附是吸热、自发的过程。吸附机理主要是FeCl₃/CTAB/RM表面的羟基（Si-OH、α-FeOOH和β-FeOOH）以及掺杂的氯原子和表面活性剂,通过物理吸附（微胶束、静电引力）和化学吸附（离子交换、氢键）有效地去除Cu(Ⅱ)离子。     

SEBS／蒙脱土复合材料结构与阻燃性能的研究

根据蒙脱土（MMT）特殊的片层结构,采用熔融插层法制备热塑性弹性体SEBS／蒙脱土插层复合材料。通过X射线衍射仪、透射电镜等表征手段研究复合材料的微观结构。使用锥形量热仪评价复合材料的燃烧性能。结果表明,有机蒙脱土（OMMT）片层的间距为1．948nm,SEBS／5％OMMT体系的片层间距为4．307nm,说明聚合物SEBS插入有机蒙脱土片层之间。SEBS／OMMT复合材料具有较低的热释放速率和质量损失速率,且随着OMMT添加量的增加,其热释放速率峰值降低愈明显。通过对复合材料的阻燃性能和微观结构的分析,探讨了其阻燃机理。     

Effects of filler geometry on internal structure and physical properties of polycarbonate composites prepared with various carbon fillers

BACKGROUND: The effects of filler geometry are important for understanding the internal structure and physical properties of polymer composites. To investigate the effects of filler geometry on electrical conductivity as well as morphological and rheological properties, three types of polycarbonate (PC) composites were prepared by melt compounding with a twin‐screw extruder. RESULTS: The electrical conductivity of PC/carbon black (CB) and PC/graphite (carbon) nanofibre (CNF) composites did not show a percolation threshold through the entire filler loading ranges. However, PC‐blend‐carbon nanotube (CNT) composites showed a percolation electrical threshold for a filler loading of 1.0 to 3.0 wt% and their maximum electrical conductivity approached 10^?3 S m^?1. PC‐blend‐CB and PC‐blend‐CNF composites showed Newtonian behaviour like pure PC matrix, but PC‐blend‐CNT composites showed yield stress as well as increased storage modulus and strong shear thinning behaviour at low angular frequency and shear rate due to strong interactions generated between CNT–CNT particles as well as PC molecules and CNT particles on the nanometre scale. CONCLUSIONS: The electrical conductivity of the PC composites with different carbon constituents was well explained by the continuous network structure formed between filler particles. The network structure was confirmed by the good dispersion of fillers as well as by the yield stress and solid‐like behaviour observed in steady and dynamic shear flows. Copyright © 2009 Society of Chemical Industry     

炭化压力对编织C/C复合材料致密过程及结构的影响

通过浸渍/高压炭化工艺在不同炭化压力下制备了高温煤沥青炭块及沥青基炭/炭（C/C）复合材料,并研究了不同炭化压力环境下对其密度和孔隙的影响.结果表明,随着炭化压力增大,沥青炭体积密度明显增加,孔隙填充效果明显改善;在编织C/C材料的致密过程中,压力越大其孔隙越小,分布越均匀,故产品致密效果越好.     

蒙脱石对OTMA的吸附研究及其复合物的结构分析

采用长碳链十八烷基三甲基氯化铵对提纯的钠基蒙脱石进行插层,研究了OTMA的吸附量随温度及时间的变化,利用XRD阐明了蒙脱石/OTMA复合物的结构特征。研究发现,温度较低有利于OTMA在蒙脱石层间及表面的吸附;80℃下,吸附反应在30~60 min内达到平衡。吸附量的增加并不一定引起层间距的增大,较高温度下OT-MA阳离子可能进入到更多的蒙脱石片层间。蒙脱石/OTMA复合物的层间距及衍射峰的相对强度随时间呈动态变化。     

Friction behaviors of carbon/carbon composites with different pyrolytic carbon textures

Friction and wear properties of carbon/carbon (C/C) composites with a smooth laminar (SL), a medium textured rough laminar (RL) and a high textured RL pyrolytic carbon texture were investigated with a home-made laboratory scale dynamometer to simulate airplane normal landing (NL), over landing (OL) and rejected take-off (RTO) conditions. The morphology of worn surfaces at different braking levels was observed with scanning electron microscopy. The results show that C/C composites with RL have nearly constant friction coefficients, stable friction curves and proper wear loss at different braking levels, while friction coefficients of C/C composites with SL pyrolytic carbon decrease intensely and their oxidation losses increase greatly under OL and RTO conditions. Therefore, C/C composites with a high and medium textured RL pyrolytic carbon may satisfy the requirements of aircraft brakes. The good friction and wear properties of C/C composites with RL are due to the properties of RL, which leads to a uniform friction film forming on the friction surface.     

Morphology and mechanical properties of nanocomposites of cellulose acetate and organic montmorillonite prepared with different plasticizers

Nanocomposites of cellulose acetate and an organically modified montmorillonite (CA/MMTO) were prepared by melt intercalation in a twin‐screw extruder, using two different plasticizers: di‐octyl phthalate (DOP) and triethyl citrate (TEC). The influence of plasticizer type and the organoclay added to the structure, the morphology, and the thermal properties of the nanocomposites was investigated. XRD and SAXS results indicated a significant CA or/and plasticizer intercalation in the clay gallery for the CA/MMTO nanocomposites. In addition, the images obtained by TEM show that the morphology of CA/MMTO nanocomposites is made up of intercalated and exfoliated silicate layers. The glass transition temperature (T_g) of CA with DOP or TEC decreased in at almost same value, which shows the characteristics of both additives as plasticizers for cellulose acetate chains. Tensile tests indicate that the nanocomposites with either of the two plasticizers presented the same performance with respect to material properties. The results demonstrated that, for some applications, TEC is an useful alternative to plasticize CA in order to substitute DOP, a non eco‐friendly plasticizer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

超临界二氧化碳中季铵盐插层改性蒙脱土的制备和结构调控

为了改善蒙脱土的层间结构、分散状态和表面形貌,在以超临界二氧化碳为媒介的环境下,利用十四烷基三甲基溴化铵对钠基蒙土进行有机插层改性,并考察了反应压强和洗涤方式对插层效果的影响。利用热重分析仪(TGA)、X射线衍射仪(XRD)、扫描电镜(SEM)和比表面积仪(BET)对样品进行分析和表征。结果表明,当温度和试剂用量一定,反应压强为20 MPa,并且采用先蒸馏水洗涤再乙醇洗涤的后处理方式时,插层效果较好。在此条件下,季铵盐成功插层到蒙脱土片层,间距由1.31 nm增加到1.70 nm,样品中仍然存在一些聚集体结构,但是颗粒粒径减小,颗粒形貌变得蓬松。     

乳状液膜分离过程中的结构演变

以乳状液膜分离H2S,借助激光粒度仪、Zeta电位仪、显微镜等手段研究乳化剂类型及浓度、内相浓度、搅拌速率和时间等因素对液膜粒径的影响。结果表明,搅拌速率及乳化剂类型对其影响最大;4种乳化剂内相粒径按照Span 80、T152、T153及T154的顺序依次增加。时间效应显示,放置24 h后,内相之间存在合并现象。通过将搅拌速度、叶轮直径、液膜密度及界面张力定义为一个Webber数(We=n2DTu3ρ/σ),能够建立其与内相粒径之间的一一对应关系,这将用于预测液膜粒径的范围。该研究对精确构建ELM分离过程中的传质模型提供了直接数据。     

硫酸改性小麦秸秆生物炭对氨氮吸附特性研究

以小麦秸秆制备生物炭(550℃)、并以硫酸作为改性剂制备得到改性生物炭材料,通过SEM、BET、元素分析、FTIR、Boehm滴定等材料学方法,发现改性后,表面出现显著的规则孔穴结构,孔径分布在0.6~1.0 nm出现集聚;比表面积较未改性组增加54%,达189.2 m~2/g;酚羟基类酸性官能团增加522%,达0.56 mmol/g。吸附性能实验显示,经济改性条件是70%硫酸反应24 h;等温吸附曲线更符合Langmuir模型,吸附量增加69%,达19.12 mg/L,吸附能力显著提高。     

Comparison of the properties of clay polymer nanocomposites prepared by montmorillonite modified by silane and by quaternary ammonium salts

In this work, the silylation of sodium montmorillonite (Na⁺-Mt, Nanofil 757®) was performed using (3-aminopropyl)triethoxy silane (APTES). Different reaction conditions were used varying the reaction time and the amount of the aminosilane. Epoxy-based nanocomposites were prepared with different amounts of silylated Mt or commercial organically modified Mt intercalated with stearylbenzyldimethyl ammonium chloride (Nanofil 2®) and distearyldimethyl ammonium chloride (Nanofil 8®), respectively. The grafting/intercalation of the aminosilane inside the Mt interlayer spaces was studied by means of Fourier transform infrared (FTIR), X-ray diffraction (XRD), nuclear magnetic resonance (NMR) and thermogravimetric analysis (TGA). After isothermal curing at 90 °C the Mt epoxy nanocomposites were analyzed by means of XRD and dynamic mechanical analysis (DMA). The glass transition temperature of all prepared nanocomposites containing silylated Mt, is slightly higher than that of the neat epoxy (2 to 5 °C). In the presence of 1 to 5 m% of silylated Mt in epoxy matrix the storage modulus increases from about 5 to 15% at 25 °C, respectively, compared to the pristine epoxy matrix, while only 0–4% increase was observed for epoxy nanocomposites with commercial modified Mt.     

Effect of exfoliated organophilic montmorillonite on the structure and conductivity of polypropylene/polyaniline composites

This study concentrates on the effect of organophilic montmorillonite (OMMT) nanolayers on conductivity, structure, morphology, and mechanical properties of the polypropylene/polyaniline (PP/PANI) composites. The composite was prepared by in situ polymerization of aniline at different composition ratios in the presence of PP powder. The structure and conductivity of ternary PP/PANI/OMMT nanocomposites were compared with those of PP/PANI composites. DC electrical conductivity measurements indicated that electrical conductivity decreased in the presence of OMMT layers. Scanning electron microscopy showed that the surface of ternary nanocomposites have more rough regions. The interaction between PANI and OMMT was confirmed by Fourier transform infrared spectroscopy. The distribution of OMMT layers in the polymer matrix, as an effective parameter on the properties of nanocomposite, was investigated and confirmed using X‐ray diffraction and transmission electron microscopy. The results showed an exfoliated array for OMMT layers in the nanocomposite structure. The shear storage modulus for PP/PANI composites was lower than that for pure PP; however, it was increased for PP/PANI/OMMT nanocomposites. The data from the tensile and izod impact strength showed that the Young's modulus and izod impact strength were increased slightly by the addition of OMMT, whereas the elongation at break was decreased. POLYM. COMPOS., 38:699–707, 2017. © 2015 Society of Plastics Engineers     

Adsorption of carbon dioxide in plasma polymers prepared from silicon compounds and carbon dioxide separation membrane

Summary Three silicon compounds, dimethyldimethoxysilane (DMDMOS), decamethylcyclopentasiloxane (DMCPS), and 1,1,3,3-tetramethyldisiloxane (TMDSO), were plasma-polymerized, and the solubility coefficient and the permeation coefficient of carbon dioxide and nitrogen gas were determined. The permeation properties of the deposited films were discussed. The plasma polymers formed from DMDMOS, DMCPS, and TMDSO showed preferential solubility for carbon dioxide. The solubility coefficient of carbon dioxide was closely related to the concentration of Si-(O-)₄ moieties in the plasma polymers. However, these plasma polymers showed no selective permeation of carbon dioxide. The diffusion process rather than the solution process controlled the permeation of carbon dioxide across the plasma polymers. Plasma polymers formed from silicon compounds, if the polymers are less cross-linked, are expected to be a good material for CO₂-selective membrane.     

Changes in the microstructure and characteristics of carbon/carbon composites with mesophase mesocarbon microbeads added during graphitization

Carbon/carbon (C/C) composites were prepared from oxidative PAN fiber felts, a resol‐type phenolic resin, and mesophase pitch derived from coal tar. In this study, the effects on mesocarbon microbeads (MCMBs), flexural strength, flexural moduli, electric conductivity, and thermal conductivity of C/C composites with a mesophase content ranging from 0 to 30 wt % were examined during pyrolysis. The results show that the C/C composite with the addition of 10–30 wt % mesophase had a higher density, greater stacking size, and higher preferred orientation than the C/C composites without any mesophase during heat treatment. These composites also exhibited an improvement in flexural strength from 19.7 to 30.3%. The flexural moduli of these composites with mesophase added increased by 15.1 to 31.3% compared to that with no mesophase added. These composites also showed improved electric conductivity, from 15.1 to 43.7%, and thermal conductivity, from 12 to 31.3%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2178–2190, 2005     

The effect of different ammonium structure of quaternary ammonium resin on the electrochemical properties

The quaternary ammonium resin is synthesized by the ring-opening reaction of an epoxy resin with a tertiary amine in the presence of a proton donor in the solution. This kind of resin can be dispersed in the water phase to form a conductible milky dispersion. In this study, different kinds of tertiary amines including the full-alkyl group and the ester group-containing or urethane group containing tertiary amine are reacted with DGEBA-type epoxy resin to synthesize the quaternary ammonium resins. The resin characteristics and the electrochemical properties of its emulsion are investigated. In addition, properties of the emulsion prepared from tertiary amine salt resin are also measured for comparison. It is found that if the substituted groups of the ammonium structure of the quaternary ammonium resin are all alkyl groups, rupture voltage of the emulsion is very low. But when one of the substituted group contains an ester group or an urethane group, rupture voltage increases remarkably and the resin can be used for electrodeposition. Meanwhile, the electrodeposition theory of quaternary ammonium resin and its thermal cross-linking reaction and the electrochemical properties of coemulsion prepared by mixing the quaternary ammonium resin and the tertiary amine salt resin are also discussed. © 1993 John Wiley & Sons, Inc.