Sol-gel preparation of a di-ureasil electrolyte doped with lithium perchlorate

Solid polymer electrolytes (SPEs) synthesized by the sol-gel process and designated as di-ureasils have been prepared through the incorporation of lithium perchlorate, LiClO₄, into the d-U(2000) organic-inorganic hybrid network. Electrolytes with lithium salt compositions of n (where n indicates the number of oxyethylene units per Li⁺ ion) between ∞ and 0.5 were characterized by conductivity measurements, cyclic voltammetry at a gold microelectrode, thermal analysis and Fourier transform Raman (FT-Raman) spectroscopy. The conductivity results obtained suggest that this system offers a quite significant improvement over previously characterized analogues doped with lithium triflate [S.C. Nunes, V. de Zea Bermudez, D. Ostrovskii, M.M. Silva, S. Barros, M.J. Smith, R.A. Sá Ferreira, L.D. Carlos, J. Rocha, E. Morales, J. Electrochem. Soc. 152 (2) (2005), A429]. “Free” perchlorate ions, detected in all the samples examined, are identified as the main charge carriers in the sample that yields the highest room temperature conductivity (n = 20). In the di-ureasils with n ≤ 10 ionic association is favoured and the ionic conductivity drops.     

AP的安全制备（英）

1 IntroductionThe ammonium perchlorate ( AP)-based compositepropellant is currently the most widely used one becausethis propellant has good burning characteristics and me-chanical properties. One of the few serious drawbacks ofthe AP-based propellant is that its products of combus-tion, which include HCl, chlorine, and chlorine oxides,cause atmospheric pollution. Increasing concern for aclean atmosphere in recent years has resulted in a com-pelling need for developing a chlorine-free,enviro…     

在苯基羧甲基亚砜体系中高氯酸铒对高氯酸铽的荧光增强效应

合成了不同摩尔比的苯基羧甲基亚砜高氯酸铽、铒异核配合物,对配合物进行了组成分析,确定了配合物组成为Tb1-xErxL2ClO4·2H2O(x=0.000～0.200,L=C6H5SOCH2COO-)。通过IR光谱的测定以及摩尔电导推测了配位情况。荧光光谱实验表明:当x=0.001～0.010时铒对铽的荧光均产生敏化增强效应,当x=0.001时敏化强度最大,可使Tb3+荧光强度增加142%。     

The study on the conductivity of styrene-maleic anhydride copolymer electrolytes based on poly(ethylene glycol)400 and LiClO4

Polyelectrolytes, in this study were synthesized from styrene-maleic anhydride (SMA) copolymer, poly(ethylene glycol)400 (PEG400), and lithium perchlorate (LiClO₄). Fourier transform infrared spectroscopy (FTIR), and magic angle spinning (MAS) solid-state NMR were used to monitor the interaction between Li⁺ ions and polymer. The results of FTIR and MAS solid-state NMR indicate the Li⁺ ions are preferentially coordinated to the ether oxygen of PEG. The T_g of the PEG segments in polyelectrolyte increases with LiClO₄ concentration, as determined by differential scanning calorimetry (DSC), indicating that solubility of the Li⁺ ions in the host polymer increases with the PEG content. Impedance spectroscopy (IS) shows that the bulk conductivity of polyelectrolytes and the conductivity behavior obeys the Vogel-Tamman-Fulcher (VTF) equation.     

Catalysis of Active Carbon Supporting Transition Metal Oxides for Pyrotechnical Reagent with Potassium Perchlorate

In order to improve the pyrotechnical reagent with potassium perchlorate,composite catalyst of active carbon supporting transition metal oxides (TMO),Fe2O3 and CuO,were prepared and added into pyrotechnical reagent with potassium perchlorate.Accelerating rate calorimeter (ARC) was used to study the catalysis of pyrotechnical reagent which is consisted of potassium perchlorate and composite catalyst.Composite catalyst of both Fe2O3 and CuO supported by active carbon can catalyze pyrotechnical reagent with potassium perchlorate.Furthermore,it can lower the apparent activation energy and accelerate the reaction with a smaller quantity than that with Fe2O3 and CuO.The maximal reaction rate of pyrotechnical reagent with potassium perchlorate mixed with Fe2O3/active carbon and CuO/active carbon is 8.31 min-1 and 9.13 min-1,which is 1.74 times and 1.91 times of pyrotechnical reagent mixed with no catalyst;time to maximal rate was 18.99 min and 1.96 min respectively,which is lower than pyrotechnical reagent mixed with no catalyst by 86.46% and 98.67% ;the apparent activation energy is 368.10 kJ·mol-1 and 325.29 kJ·mol-1,which is lower than pyrotechnical reagent mixed with no catalyst by 31.89% and 39.81% respectively.     

Specific features of thermal decomposition of ammonium perchlorate subjected to γ radiation

Results of studying thermal decomposition of ammonium perchlorate (AP) samples in the original form and after irradiation by γ-quanta of ⁶⁰Co by methods of differential scanning calorimetry and dynamic thermogravimetry with heating rates b = 0.1–0.3 K/sec are described. Irradiation is performed in air at a temperature of 298 ± 2 K and a dose rate of ≈0.2 Gy/sec in the range of absorbed doses D = 0–150 kGy. Preliminary irradiation is demonstrated to lead to substantial transformations of the pattern of thermal decomposition of ammonium perchlorate in the dynamic regime of heating: the single-stage process of decomposition of non-irradiated samples proceeding at b = 0.107 K/sec in the temperature range of 625 to 743 K is replaced by a multistage process. At D = 150 kGy, exothermal transformations accompanied by noticeable losses of sample mass are observed starting from 473 K. Within experimental errors, the total thermal effect of AP decomposition is found to be independent of the absorbed dose and amounts to −1150 kJ/kg on the average. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 69–74, November–December, 2007.     

Taguchi Optimization of Solvent-Antisolvent Crystallization to Prepare Ammonium Perchlorate Particles

The sphericity and size of ammonium perchlorate (AP) particles significantly influence the properties of composite propellants. As the AP particles become more spherical, the accumulation coefficient increases, the viscosity during casting decreases, and the particle loading and burning rate increase. Hence, the production of micronized AP particles with an average size between 1 and 20 μm is important to increase the loading percentage of AP in the composite propellant. Here, the Taguchi experimental design was used to optimize the solvent-antisolvent crystallization (SAC) process for the preparation of micronized AP particles with higher sphericity. SAC parameters such as the type of antisolvent, the solvent-to-antisolvent ratio, the antisolvent temperature, the stirring speed, and the retention time were investigated at four levels. The type of antisolvent and the solvent-to-antisolvent ratio were found to mainly contribute to improving the sphericity and size of the AP particles, respectively.     

溶剂热法合成花状Co_3O_4微球及其对高氯酸铵热分解的催化作用

以醋酸钴为原料,在甲醇体系中采用溶剂热法合成了由纳米片自组装而成的花状(CH_3O)_2Co前驱体微球。将前驱体焙烧后,得到了形貌保持良好的花状多孔Co_3O_4微球。利用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、热重(TG)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和N_2吸附-脱附等手段对样品的物相、化学组成、形貌及孔结构进行了表征。采用差示扫描量热(DSC)技术评价了Co_3O_4花状微球对高氯酸铵(AP)的热分解催化作用。结果表明,花状Co_3O_4微球对AP热分解过程具有良好的催化活性,添加2%(质量分数)的Co_3O_4可使AP的高温分解峰值温度降低122℃,表观分解热提高422 J/g。优异性能的发挥归因于其良好的分散性和丰富的级次孔结构。     

溶胀/溶解法回收HTPB推进剂中AP组分的实验研究

采用溶胀/溶解法回收报废HTPB推进剂中的AP。研究了浸取时间、浸取温度、四氢呋喃质量分数、液料比(四氢呋喃溶液体积与HTPB推进剂的质量比)、试样厚度及搅拌速率对AP回收率的影响。通过扫描电镜、X射线能谱仪对回收得到的AP进行表征,并对其纯度进行了检测。结果表明,AP的最佳回收工艺参数为:浸取时间6h、浸取温度60℃、四氢呋喃质量分数80%、液料比10∶1(mL/g)、试样厚度3mm、搅拌速率500r/min。其中,浸取时间、浸取温度和四氢呋喃质量分数对AP回收率的影响较大。在最佳工艺条件下,AP的回收率为95.0%,纯度为96.1%,表明此方法可用于报废HTPB推进剂中AP组分的回收。     

NH4NO3和NH4ClO4的绝热分解研究

用加速热量仪研究了硝酸铵和高氯酸铵的热分解过程,得到了它们的绝热分解温度和压力随时间的变化曲线,并分别计算了这两种物质的动力学参数表观活化能和指前因子。