The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

Nanobubble generation and its applications in froth flotation (part Ⅲ): specially designed laboratory scale column flotation of phosphate

Froth flotation is used widely for upgrading raw phosphate. The flotation recovery of coarse phosphate (-1.18+0.425 mm) is much lower than that achieved on the -0.425+0.15 mm size fraction. Enhanced recovery of coarse phosphate particles is of great economic and environmental importance for phosphate industry. In this investigation, four different phosphate samples were aquired, characterized and tested in a specially designed laboratory-scale flotation column. Significant recovery improvement of coarse phosphate flotation was achieved using cavitation-generated nanobubble though its effects differ among the four testing phosphate samples. The laboratory-scale flotation column test results indicate that nanobubble increased P2O5 recovery by up to 10%-30% for a given Acid Insoluble (A.I.) rejection, depending on the characteristic of phosphate samples. The improvement ef-fect of nanobubble on the hard-to-float particles was more significant than that on easy-to-float particles, especially at lower col-lector dosages. Nanobubbles reduced the collector dosage by 1/3 to 1/2. Nanobubbles almost doubled the coarse phosphate flotation rate constant and increased the flotation selectivity index by up to 25%.     

Solid state interfacial reactions in electrodeposited Ni/Sn couples

Ni/Sn couples,prepared by sequentially electroplating Ni layers and Sn layers on metallized Si wafers,were employed to study the mierostructures and growth kinetics of Ni-Sn intermediate phases,when the Ni/Sn couples were aged at room temperature or annealed at temperatures from 150 to 225℃for various times.The results show that the NiSn phase and Ni_3Sn_4 phase are formed,respectively,in the aged couples and annealed couples.The Ni_3Sn_4 layer is continuously distributed between the Ni and Sn sides in t...     

三种生物质的热解动力学研究

为进一步研究生物质的热解动力学,在氮气气氛和不同的加热速率下对马尾松、棉杆和杉木试样进行了热分析实验.结果表明,由于生物质中矿物质对热解的催化作用,灰分含量越高,热解温区越低;用占生物质质量约10%的碳酸钠对生物质进行处理后,其热解温区也明显降低;用Ozawa-Flynn-Wall法计算的活化能随转化率的增加而增加,这是由于生物质中不同成分如半纤维素与纤维素等的热解特性不同所致;联合运用Satava法和Ozawa-Flynn-Wall法确定了低温区和高温区热解的最佳机理函数,发现Avrami-Ero-feev方程、Jander方程和Zhuralev,Lesokin and Tempelmen(Z-L-T)方程分别可以用来很好地描述不同温区的热解过程.热解机理是随机成核和随后生长或三维扩散.除了高温催化段以外,在其他温区用两种方法计算的活化能均很接近.     

二价铁离子对零价铁还原硝基苯的影响

为了解地下水环境中铁离子对零价铁(zero valention)还原作用的影响,采用批次实验,研究不同质量浓度二价铁离子对ZVI还原硝基苯的影响,利用HPLC和GC-MS作为分析工具,观测反应过程中硝基苯的质量浓度,同时跟踪溶液中Fe2+、pH、ORP的变化.结果表明,有无Fe2+存在,硝基苯均可被ZVI还原为苯胺,Fe2+没有改变还原产物;溶液中投加Fe2+后,ZVI还原硝基苯的反应速率明显加快,溶液中Fe2+对于还原反应起促进作用;溶液中Fe2+对ZVI体系pH起缓冲作用,含有Fe2+的ZVI体系ORP下降明显.反应动力学分析表明,硝基苯的还原反应符合假一级动力学模型,表观速率常数kobs值随Fe2+质量浓度的升高而增加,Fe2+离子的存在有助于ZVI对硝基苯的还原.     

光谱法研究Ni[S2P（OCH2CH2Ph）2]2与α,α＇-联吡啶加合反应

利用紫外光谱法研究了Ni[S2P（OCH2CH2Ph）2]2与α,α-联吡啶的加合反应。研究发现Ni[S2P（OCH2CH2Ph）2]2与α,α-联吡啶形成1∶1型加合物,在25℃的苯溶剂中,加合物的离解度α=0.07,稳定常数K稳^θ=2.1×10^6。     

巴洛沙星的合成研究

巴洛沙星是一种新型喹诺酮类抗感染药物。从反应温度、反应时间、反应物料摩尔配比和反应溶剂等对合成的影响进行了详细研究。结果表明,其优惠工艺合成条件为:以S1为溶剂,反应温度40℃,反应时间4 h,反应物料摩尔配比n螯合物Ⅰ∶nMAP=1∶1,产品收率79.5%,含量91.4%。     

无机分离膜

本文综述了无机膜的结构及特性,无机膜的分离机理、无机膜的制备方法。介绍了常见的几种无机膜及其在气体、液体以及生化产品的分离、废水处理、啤酒、饮料的滤菌、海水淡化等领域中的应用。展望了无机膜在硫化氢分解制氢、丙烷、环己烷和乙苯脱氢等反应中实现反应分离一体化的前景。     

Change in the molecular weight distribution of poly(ethylene oxide) caused by the complexation with poly(acrylic acid)

The complexation between poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) was made by using double the molar quantity of either polymer component at pH 2 where the resulting complex completely precipitates. After the removal of the precipitate, PEO or PAA remaining in the supernatant was subjected to gel permeation chromatography to investigate the change in the molecular weight distribution (MWD) caused by the complexation. No remarkable difference is observed in the MWD curves for PEO[1] (M_w=1.37 × 10⁴) before and after the complexation with PAA[1] (M_w=1.10 × 10³) and PAA[2] (M_w=4.16 × 10⁵). However, the MWD curves of PEO[2] (M_w=1.26 × 10⁵) and PAA[2] become shortened and shift to the low molecular weight side after the complexation with PAA[1] or [2] and PEO[2], respectively. This tendency is enhanced by increasing the complexation temperature. From these results, it is indicated that the complexation between PEO and PAA deals with an equilibrium reaction, and the equilibrium constant is dependent on the chain length of both polymer components and also on the complexation temperature.     

Kinetics of Slag Hydration in the Presence of Calcium Hydroxide

The reaction between ground granulated blast furnace slag (GGBFS) having an empirical formula of C_7.88S_7.39M₃A and calcium hydroxide (CH) was investigated. The kinetics of the reaction were explored. Thermogravimetric analysis was used to monitor the consumption of CH from which rate constants were determined. Based on Knudsen's kinetic model, activation energies of 14.5, 17.9, and 22.6 kJ/mol were determined for three different mass ratios of slag and CH reacted over a temperature range of 15° to 50°C and hydrated for a period of time from 0 to 32 days. A comparison of the kinetics of the slag/CH reaction was made with slag/portland cement hydration. The basic features of both appear similar.