机械激活矿渣水泥

用于式高能振动磨机械激活矿渣（炉渣和／或硅灰）水泥。研究表明：经机械激活后．矿渣水泥的颗粒粒度降低，颗粒的比表面积增大。在掺合了矿渣的水泥中硅微粒聚团经机械激活后可有效地分散并作用于水泥中．使矿渣水泥的水化反应括性增强，促进水泥水化反应，降低水泥制品的孔隙度．从而可以提高水泥制品的力学性能。通过Fourier变换红外光谱和核磁共振等方法分析了机械激活作用的机理。     

Upgrading of gas oils: the HDS kinetics of dibenzothiophene and its derivatives in real gas oil

The hydrodesulphurization (HDS) of dibenzothiophene (DBT), 4-methyl dibenzothiophene (4 M-DBT), 4,6-dimethyl dibenzothiophene (4,6 DM-DBT) and 4,6-diethyl dibenzothiophene (4,6 DE-DBT) as real gas oil components on NiMo/Al₂O₃ catalyst was investigated. On the basis of the first order rate constants of HDS of the individual sulphur compounds reactivities of the investigated compounds decreased in the order DBT ≫ 4 M-DBT > 4,6 DE-DBT ≈ 4,6 DM-DBT. Apparent activation energies of HDS of above sulphur compounds increased from 80.0 to 120.5 kJ/mol.     

Removal of chromium (VI) from dilute aqueous solutions by activated carbon developed from Terminalia arjuna nuts activated with zinc chloride

Different structured activated carbons were prepared from Terminalia arjuna nuts, an agricultural waste, by chemical activation with zinc chloride for the adsorption of Cr(VI) from dilute aqueous solutions. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor, g/g). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. A high surface area of was obtained at a chemical ratio of 300%, carbonization time and temperature of 1 h and 500 °C, respectively. The activated carbon developed shows substantial capability to adsorb Cr(VI) from dilute aqueous solutions. The parameters studied include pH, adsorbent dosage, contact time, and initial concentrations. The kinetic data were best fitted to the Lagergren pseudo-first-order model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. The maximum removal of chromium was obtained at pH 1.0 (about 99% for adsorbent dose of 2 g/l and 10 mg/l initial concentration).     

Study on the synthesis of thiirane

In this study, a thiirane resin was synthesized by the reaction of corresponding epoxy resin with KSCN. The synthetic conditions influencing the conversion of epoxy group were systematically investigated, such as the reaction temperature, reaction media, reaction time and the ratio of KSCN to epoxy group. It was found that the conversion of epoxy group increased with the increasing reaction temperature, improving the solubility of the mediate, extending reaction time, and the enhancing ratio of salt (KSCN) to epoxy group. Wherein, the reaction temperature and the ratio of the KSCN to epoxy group were more effective. For example, when the molar ratio of KSCN to epoxy group was equal to 2.0, the conversion of epoxy group got the maximum value, 0.65. In addition, the hot plate method was used to measure the gelling time of the resultant thiirane resin at different temperatures. It was found that the gelling time was reduced to 47–85% times as the corresponding epoxy resin depending on the conversion of the epoxy group, and the curing activation energy was diminished from 39 kJ/mol of epoxy resin to 17 kJ/mol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4023–4027, 2006     

Effect of hydrophobic hexafluoroisopropylidene group on the water sorption behaviors of rigid poly(p‐phenylene pyromellitimide) polyimide thin films

We prepared poly(p‐phenylene pyromellitimide) (PMDA–PDA), poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide), and their copolyimides with various compositions to explore the relationship between the water sorption and structure. The water sorption behaviors were gravimetrically investigated as a function of composition and temperature and interpreted with a Fickian diffusion model in films. Overall, the water sorption behaviors were strongly dependent on the changes in morphological structure, which originated from the variations in composition. When the content of the bulky hexafluoroisopropylidene group (6FDA) was increased, the water uptake decreased from 5.80 to 3.18 wt %, whereas the diffusion coefficient increased from 3.6 × 10^?10 to 11.3 × 10^?10 cm²/s. The relatively high water uptake in the PMDA–PDA polyimide film was successfully healed by the incorporation of 6FDA, which may have resulted from the increases in the intermolecular packing order and hydrophobicity. The degree of orientation and crystallinity, which are in‐plane characteristics, were directly correlated to the diffusion coefficient and activation energy in the polyimide film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3442–3446, 2003     

Kinetic study of radical polymerization. II. Solid‐state bulk polymerization of sodium methacrylate by differential scanning calorimetry

The solid‐state radical polymerization of sodium methacrylate was investigated. It was initiated by azobisisobutyronitrile, which was used as a radical initiator. Differential scanning calorimetry (DSC) was used to observe the endothermic and exothermic transitions during the polymerization reaction. Structural studies were performed with the DSC thermograms and Fourier transform infrared and ultraviolet–visible spectra, and all of the results confirmed the progress of the reaction. The obtained data revealed that the polymerization reaction proceeded completely with a 100% conversion. ΔH of this reaction was calculated with various amounts of the initiator, and the peak temperatures were determined at different heating rates. The activation energy (19.7 kcal mol^?1) was also obtained by the Kissinger method for this type of solid polymerization reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1648–1654, 2003     

纳米碳酸钙的表面活化改性研究

本文主要介绍通过加入特定的表面改性剂,制得了表面改性的活性碳酸钙.并对活化过程中的一系列影响因素,如活化温度、活化时间、碳酸钙悬浊液浓度、表面改性剂用量进行了研究.     

Methane activation without using oxidants over Mo/HZSM-5 zeolite catalysts

The effect of Mo loading, calcination temperature, reaction temperature and space velocity on the catalytic performance of methane dehydrogenation and aromatization without using oxidants over Mo/HZSM-5 has been studied. The XRD and BET measurements show that Mo species are highly dispersed in the channels of the HZSM-5 zeolite, resulting from the interaction between the Mo species and the zeolite, which also leads to a decrease in its crystallinity. The Brønsted acidity, the channel structure and the state and location of Mo species in the zeolite seem to be crucial factors for its catalytic performance. It was found that 2% Mo/HZSM-5 calcined at 773 K showed the best aromatization activity among the tested catalysts, the methane conversion being 9% at 1013 K with the selectivity to aromatics higher than 90%. The experimental results obtained from the variation of space velocity gave evidence that ethylene is an initial product. On the basis of these results a possible mechanism for methane dehydrogenation and aromatization has been proposed in which both the heterolytic splitting of methane in a solid acid environment and a molybdenum carbene-like complex as an intermediate are of significance.     

A vibrational study of the activation sequence of C–H and C–C bonds of isobutene and 1-butene on Mo(110) and (4 × 4)-C/Mo(110) surfaces

The thermal decomposition pathways of isobutene and 1-butene on both Mo(110) and 4 × 4-C/Mo(110) surfaces have been studied using high-resolution electron energy loss spectroscopy (HREELS) in order to highlight the substantially different activities of these two surfaces towards the cleavage of C–H and C–C bonds. On clean Mo(110), the CH₂ group of isobutene decomposes upon heating to 150 K, producing either a /-bonded isobutenylidene [(CH₃)₂CCH] species or a 1,1-di-/-bonded isobutenyl [(CH₃)₂CC] species. Upon further heating, extensive C–H bond scission occurs to form hydrocarbon fragments which do not contain CH₃ or CH₂ groups, but appear to have largely intact carbon skeletons. By contrast, isobutene is molecularly adsorbed on the carbide-modified surface at 150 K. Further heating produces isobutylidyne [(CH₃)₂HCC] by 300 K, which subsequently decomposes via C–C bond scission to generate surface methyl groups. The different activation sequence of the C–H and C–C bonds of isobutene on clean and carbide-modified Mo(110) surfaces is also qualitatively confirmed by comparative studies of 1-butene on the two surfaces.     

Pulse study of methane partial oxidation to syngas over SiO2-supported nickel catalysts

Methane was pulsed over pure CuO and NiO as well as Cu/La₂O₃ and Ni/La₂O₃ catalysts at 600° C. Results indicate that the mechanisms for methane activation over copper and nickel are quite different. Over CuO, methane is converted to CO₂ and H₂O, most likely via the combustion mechanism; whereas metallic copper does not activate methane. Over NiO in the presence of metallic nickel sites, methane activation follows the pyrolysis mechanism to give CO, CO₂, H₂ and H₂O. Similar results were obtained over the Cu/La₂O₃ and Ni/La₂O₃ catalysts. XRD investigations indicate that copper and nickel existed as CuLa₂O₄ and LaNiO₃ respectively in the La₂O₃-supported catalysts. The effect of La₂O₃ on the activation of methane is discussed.