Ultrasound as a Tool to Synthesize Nano-Sized Silica–Alumina Catalysts with Controlled Mesoporous Distribution by a Novel Sol–Gel Process

A novel sol–gel process is used to synthesize mesoporous silica–alumina catalysts with controlled pore size distribution without using templates or pore-regulating agents. The nitrogen sorption analysis shows that the synthesized materials have high specific surface area in the range 587–692 m²/g and similar mesoporous distribution within 2–11 nm. Ultrasound is applied to prepare precursor silica–alumina sol with narrow particle diameter distribution. By calculation, it is found that ultrasonic treatment is able to provide 22.94 kJ/mol energy, which is just in accordance with the weak bond's bonding energy. Based on the calculation result, it is proposed that the role of ultrasonic treatment followed by acid peptization is to provide energy to break down the weak bonds. After gelation, the regular and close packing of similar-sized sol particles is capable of formation of controlled-sized interstices which are the precursors of mesopores. Solid-state ²⁷Al MAS NMR and TEM are used to characterize the samples' structure and particle morphology. They show that most of the aluminum is located in the tetrahedral position in the present materials. According to TEM results, it is shown that the synthesized materials have spherical particles with size of about 15 nm.     

微波辐射对甲苯磺酸催化合成乙酸环己酯

以冰醋酸和环己醇为原料 ,环已烷为带水剂 ,对甲苯磺酸作催化剂 ,采用微波辐射技术 ,在常压下直接合成乙酸环己酯。最适宜反应条件为 :n(环己醇 )∶n(乙酸 ) =1 5∶1 0 ,对甲苯磺酸用量 0 2 0 g ,带水剂用量 5mL ,微波功率 5 95W ,辐射时间 15min ,产率达 97%以上     

微波辅助合成1-(3-羟丙基)-4-哌啶酮

以3-羟基丙胺和丙烯酸甲酯为起始原料,在微波辅助下进行Michael加成、Dieckmann环合和脱羧反应合成了1-(3-羟丙基)-4-哌啶酮.并对Michael加成、Dieckmann环合和脱羧反应的工艺参数进行了优化,通过核磁共振波谱对目标化合物和中间体的结构进行表征.得到的最优Michael加成工艺条件为:n(3-羟基丙胺):n(丙烯酸甲酯)=1.0:2.4,微波辐射功率为120 W,反应温度40℃,反应时间30 min.在该条件下制备3-[(2-甲氧羰乙基)(3-羟丙基)氨基]丙酸甲酯的收率为92.6％;在微波辐射功率为200 W下,Dieckmann环合反应和脱羧反应分别为20和25 min,以88.5％的收率得到1-(3-羟丙基)-4-哌啶酮;目标产物总收率为82.0％.     

Influence of untreated and novel electron‐beam‐modified surface‐coated silica filler on the thermorheological properties of ethylene–octene copolymer

We developed surface‐modified silica fillers by coating these with an acrylate monomer, trimethylolpropane triacrylate, or a silane coupling agent, triethoxyvinyl silane, followed by electron‐beam irradiation at room temperature. These were incorporated in an ethylene–octene copolymer rubber. Thermorheological studies of the unvulcanized ethylene–octene copolymer and its untreated and modified silica‐filled composites were done with a shear dynamic oscillating rheometer. Modification of the silica filler, especially via the silanization process followed by electron beam treatment, significantly reduced filler–filler networking as revealed from the log–log plots of storage modulus and complex shear viscosity, and its real component. The rheological complexity of the compositions was analyzed from a double logarithmic plot of the storage modulus and loss modulus. The results obtained from the master curves constructed on the basis of the time–temperature superposition principle and the activation energy calculated from the Arrhenius equation for the flow of above these compounds further supported these findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2453–2459, 2003     

Physicochemical properties of irradiated and loaded LDPE films with polyfunctional monomers

Polyfunctional monomers (PFMs), namely, trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate were blended with low‐density polyethylene (LDPE) and exposed to different doses of EB irradiation. Fourier transform infrared and ultraviolet and UV–vis spectroscopy of the unirradiated, irradiated, unloaded, and PFMs‐loaded LDPE films were studied under various irradiation doses up to 300 kGy. The degree of crosslinking and oxidative degradation, as measured by the spectroscopic parameters, were dependent on both the irradiation dose and the type of loaded PFMs. For all of the loaded monomers, the extent of crosslinking increased at different rates as a function of irradiation dose. TMPTMA monomer was the most efficient in enhancing the crosslinking of LDPE films compared to the other loaded monomers. However, the unloaded LDPE film showed the least extent of crosslinking. In addition, the EB‐radiation‐induced changes, such as trans‐vinylene formation, a decrease in vinyl and vinylidene unsaturation; and carbonyl double‐bond formation and change in crystallinity were correlated. The importance of these results on the prediction of the role of polyfunctional monomers in the production of crosslinked polymers is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2025–2035, 2003     

Impact of H+ ion irradiation on Matrimid®. I. Evolution in chemical structure

Ion beam irradiation can be used to modify the structure and gas transport properties of glassy polymers. This is the first of two studies that focus on the impact of H⁺ ion irradiation on the structure and permeation properties of the polyimide Matrimid®. Specifically, the evolution in chemical structure after H⁺ irradiation over a range of fluences was analyzed using FTIR spectroscopy and dissolution studies. Although H⁺ ion irradiation at very low ion fluences induced little modification in the chemical structure, irradiation at relatively high ion fluences resulted in crosslinking of the irradiated films. The branched structure of the aliphatic methyl (CH₃) was the most sensitive to the H⁺ ion irradiation. The para‐disubstituted aromatic ring showed the strongest resistance toward ion irradiation and required fairly high doses to induce degradation. Two potential crosslinking mechanisms related to the degradation of the aliphatic methyl and the benzophenone carbonyl were presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2010–2019, 2003     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

<Emphasis Type="Italic">In situ</Emphasis> monitoring of solid fat content by means of pulsed nuclear magnetic resonance spectrometry and ultrasonics

An ultrasonic technique was developed to study the crystallization process of edible fats on-line. A chirp wave was used instead of the conventional pulser signal, thus achieving a higher signal-to-noise ratio. This enabled measurements to be made in concentrated systems [≈20% solid fat content (SFC)] through a 8.11-cm thick sample without significant signal loss. Fat samples were crystallized at 20, 25, and 30°C at a constant agitation rate of 400 rpm for 90 min. The crystallization process was followed by ultrasonic spectroscopy and a low-resolution pulsed nuclear magnetic resonance spectrometer. Specific relationships were found between ultrasonic parameters [integrated response, time of flight (TF), and full width half maximum] and SFC. TF, which is an indirect measurement of the ultrasonic velocity (v), was highly correlated to SFC (r ²>0.9) in a linear fashion (v=2.601 SFC+1433.0).     

高强混凝土受火后力学性能变化规律的研究

对受火后的混凝土试件进行了抗压强度、抗折强度和劈裂抗拉强度试验,讨论了温度、强度等级、试件尺寸、含水量对其高温后力学性能的影响。研究表明,受火后,抗折强度较抗压强度下降更快;高强度的混凝土在600℃前抗压强度下降不多;大尺寸混凝土试件较小尺寸混凝土试件的残余抗压强度下降慢;混凝土试件的含水率越高,相对残余抗压强度越低。采用超声波速度法和质量损失法对火灾高温后混凝土内部结构的变化进行了探讨。     

Ultrasonic oscillations effect on rheological and processing properties of metallocene‐catalyzed linear low density polyethylene

The effects of ultrasonic oscillations and die materials on die pressure, productivity of extrusion, melt viscosity of metallocene‐catalyzed linear low density polyethylene (mLLDPE), as well as their mechanism were studied in a special ultrasonic oscillations extrusion system developed in our lab. Die materials used in our experiment included steel, brass, and polytetrafluoroethylene (PTFE)_. The experimental results showed that ultrasonic oscillations as well as die materials have great influence on the rheological and processing behavior of mLLDPE. Ultrasonic oscillations can greatly increase the productivity of mLLDPE melt extruded through different dies, and can decrease the die pressure and the melt viscosity of mLLDPE. Compared with steel or brass die, mLLDPE melt extruded through PTFE die is more sensitive to ultrasonic oscillations. A possible mechanism for the improved processability of mLLDPE is proposed in this article. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1873–1878, 2003