Alkali Dinitramide Salts. Part 1: Synthesis and Characterization

Starting from commercially available ammonium dinitramide (ADN), which was dissolved either in water or in methanol, the sodium, potassium, rubidium and cesium dinitramide were synthesized in yields >70% by adding the corresponding alkali metal hydroxide. The basic equation for the reaction is the following:     

Synthesis of Porous NiO and ZnO Submicro- and Nanofibers from Electrospun Polymer Fiber Templates

Porous nickel oxide (NiO) and zinc oxide (ZnO) submicro- and nanofibers were synthesized by impregnating electrospun polyacrylonitrile (PAN) fiber templates with corresponding metal nitrate aqueous solutions and subsequent calcination. The diameter of the NiO and ZnO fibers was closely related to that of the template fibers and larger diameters were obtained when using the template fibers with larger diameter. SEM results showed that the NiO and ZnO fibers have a large amount of pores with diameters ranging from 5 nm to 20 nm and 50 nm to 100 nm, respectively. Energy dispersive X-ray (EDX) spectra and X-ray diffraction (XRD) patterns testified that the obtained materials were NiO and ZnO with high purity.     

Macroporous metal oxide foams through self-sustained combustion reactions

A number of macroporous metal oxide foams were prepared through self-sustained combustion reactions starting from dough made of the corresponding metal nitrate, urea and starch. The nitrate ion acts as an oxidizing agent, urea as fuel and starch as an organic binder. The metal oxide foams are characterized by scanning electron microscopy and powder X-ray diffraction.     

废弃选择性催化还原催化剂混掺对新催化剂脱硝性能的影响

采用"混炼-挤出-干燥-煅烧"工艺制备了不同废弃选择性催化还原（SCR）催化剂混掺比例的新催化剂样品,在自制实验台架上进行了脱硝性能和脱硝寿命评估实验。实验表明,当废催化剂混掺比例小于5%时,样品脱硝性能相比无混掺样品有轻微下降,催化剂脱硝效率随运行时间的衰减速率正常;当混掺比例大于5%时,催化剂样品脱硝性能大幅衰减,催化剂寿命缩短。结合N₂吸附-脱附、扫描电子显微镜（SEM）、X射线荧光光谱（XRF）、X射线衍射（XRD）等表征手段分析,废催化剂的掺入会将碱金属、As等有害物质带入到高混掺量的样品中,导致催化剂脱硝性能下降;混掺比例高达15%时,15-cat样品表面复杂程度大幅下降,不利于SCR反应进行。实验论证了较高废弃催化剂混掺比例会严重影响制备所得新催化剂的脱硝性能。     

1-氨基-1-肼基-2,2-二硝基乙烯碱金属盐的制备及对改性双基推进剂主组分热分解的催化作用

1-氨基-1-肼基-2,2-二硝基乙烯（AHDNE）与氢氧化钾或碳酸铯反应得到相应的碱金属盐AHDNE-K 和AHDNE-Cs。 通过元素分析和红外光谱对其进行结构表征;采用单晶X射线衍射分析法测定了AHDNE-K的单晶结构,DSC技术研究了两种金属盐对3种改性双基推进剂主组分HMX、RDX和NC/NG热分解的影响。结果表明,AHDNE-K对NC/NG有明显的催化效果,使分解温度降低了约24 ℃,能量增加了1 316 J·g^-1。     

Alkali‐Dinitramide Salts Part 2: Oxidizers for Special Pyrotechnic Applications

Ammonium dinitramide is planned to be a substitute for commonly used oxidizers in rocket motor compositions. Different teams worldwide have already synthesized alkali salts of dinitramide and several times it was used as an oxidizer for pyrotechnic compositions containing boron as a reducing agent. In this paper the results of a systematic investigation to characterize the pyrotechnic redox systems titanium/potassium dinitramide and titanium/cesium dinitramide are presented and the data are compared. The heats of reaction as well as the burning rates of the redox system titanium/potassium dinitramide are higher than those of the redox system titanium/cesium dinitramide. Both systems show a moderate sensitivity to friction and electrostatic discharges. However the sensitivity of mixtures of both redox systems shows a very high sensitivity to impact. These sensitivities are in the range of pure HMX or pentaerythritol tetranitrate.     

碱木质素接枝聚丙烯腈多孔材料的性能表征

在碱木质素与丙烯腈单体接枝共聚过程中分别添加无机模板剂硝酸铵、硝酸铁和氯化钠制备碱木质素接枝聚丙烯腈 (AL-g-PAN)多孔材料。利用SEM、XRD对AL-g-PAN的结构进行表征;以FT-IR对材料的官能团进行分析;以TG-DTG、DSC对AL-g-PAN的热性能进行测定。以硝酸铅为目标污染物,考察了多孔AL-g-PAN对Pb²⁺的吸附性能。结果表明:在25 ℃、Pb²⁺初始浓度为308.5 mg/L、pH值为5的条件下,以硝酸铁为模板剂制备的多孔AL-g-PAN对Pb²⁺平衡吸附量为145.83 mg/g,Pb²⁺去除率为94.5%;该多孔材料成孔均匀、平均孔径在0.913 nm、孔径主要分布在2 nm以下的微孔区域;相同条件下,无模板剂的碱木质素接枝聚丙烯腈对Pb²⁺平衡吸附量仅为28.06 mg/g,其去除率为18.2%。多孔AL-g-PAN的热稳定性较碱木质素明显增强。     

Synthesis of pure phase BiFeO3 powders in molten alkali metal nitrates

Pure phase BiFeO₃ powders were successfully synthesized in molten alkali metal nitrates (KNO₃–NaNO₃) at 500 °C. The as-prepared BiFeO₃ had a rhombohedral structure which was studied using X-ray diffraction. The plate-like morphologies were investigated through scanning electron microscopy and transmission electron microscopy. The average length and width of BiFeO₃ plates were 400 and 200 nm, respectively. Furthermore, the mechanism of formation of BiFeO₃ was also discussed through X-ray diffraction, thermogravimetry, differential thermal analysis and mass spectrometry.     

Structural study of cellophane

Fine structural aspects of cellophane have been investigated using X-ray and electron diffraction techniques as well as a kinetic study of the dissolution of cellophane in 0.5 M cupriethylene diamine solution. The X-ray diffraction pattern for cellophane shows a typical cellulose II structure while the electron diffraction pattern highlights a typical cellulose I structure with very weak reflection for a cellulose II type lattice. The kinetics study of cellophane dissolution in cupriethylene diamine confirms the presence of these polymorphic forms of cellulose in cellophane. The paper also reports studies of the X-ray and electron diffraction patterns of cellophane in relation to crystallite size and degradation under electron beam. It is shown that the observed anomaly between the X-ray and electron diffraction patterns of cellophane is a consequence of (i) the larger minimum crystallite size requirement for producing diffraction patterns with X-rays than with the electron beam (ii) the much faster degradation of cellulose II crystallites than that of cellulose I crystallites under the electron beam and (iii) the reduction in the crystallite size of cellulose II in cellophane from that in wood pulp alkali cellulose during the process of regeneration.     

The effect of the ethylene glycol to metal nitrate molar ratio on the phase evolution,morphology and magnetic properties of single phase BiFeO3 nanoparticles

In this work, single phase BiFeO₃ nanoparticles have been synthesized by thermal decomposition of a glyoxylate complex achieved by the redox reaction between ethylene glycol and nitrate anions. The effects of different molar ratios of ethylene glycol to metal nitrate anions on the phase evolution, morphology and magnetic properties were investigated by infrared spectroscopy, thermal analysis, X-ray diffraction, electron microscopy and vibrating sample magnetometry methods. The single phase bismuth ferrite nanoparticles synthesized with the ethylene glycol to nitrate anions molar ratio of 5 showed the weak ferromagnetism behavior with saturation magnetization of 1.3 emu/g, due to the size confinement effect. Furthermore, the BiFeO₃ nanoparticles were used for the degradation of methylene blue (MB) as a typical dye pollutant under direct sunlight irradiation.     

Application of impregnation combustion method for fabrication of nanostructure CuO/ZnO composite oxide: XRD,FESEM, DRS and FTIR study

Nanostructured CuO/ZnO composite oxide was prepared by a novel impregnation combustion method using copper nitrate and zinc oxide tetrapod. The X-ray diffraction patterns revealed that CuO/ZnO composite oxide was formed. The effects of different impregnation combustion parameters on the properties of composite were studied by field-emission scanning electron microscope (FESEM), powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) and UV–vis diffuse reflectance spectrum (DRS). The synthesis of ZnO–CuO nanocomposites through impregnation of a zinc oxide tetrapod with copper nitrate aqueous sodium carbonate solutions is reported. During thermal treatment the samples evolve toward the formation of nanocrystalline ZnO particles (zincite phase) dispersed onto tenorite, CuO annealed at 450 °C. XRD patterns of the precursors calcined at 450 °C showed the formation of the zincite–tenorite phases. Field emission scanning electron microscopy (FESEM) exhibited loosely agglomerated hexagonal particles with uniform morphology having a size around 50 nm.     

纤维素蒸汽闪爆改性前后的溶解性能及结构表征研究

采用蒸汽闪爆技术对天然纤维素进行改性处理,对处理前后的纤维素进行了溶解度测试、SEM及X-射线衍射分析,研究表明,蒸汽闪爆破坏了纤维素分子内氢键,使改性后的天然纤维素在一定温度下可直接完全溶解于特定浓度的NaOH水溶液中,且适当润胀剂的加入也有利于纤维素在NaOH水溶液中的溶解。     

碱激发胶凝材料的反应产物

通过X射线衍射、红外光谱、扫描电子显微镜、能谱分析,对碱激发胶凝材料反应产物的相组成进行探索性分析.结果表明:该碱激发胶凝材料硬化后的反应产物主要是含碱的铝硅酸盐凝胶,并存在未反应的水玻璃,副产物K2SO4是生产物中唯一的晶体物质.含碱的铝硅酸盐凝胶中可固溶Mg,Ca,S,Fe等离子,包裹着起微集料作用的未反应的粉煤灰玻璃微珠与莫来石颗粒,形成高度非均质的复杂体系.     

燃煤可吸入颗粒的物理化学特性及形成机理

应用低压撞击器分别对某100 MW和50 MW燃煤机组锅炉的除尘器前后飞灰颗粒进行采样,研究了除尘器前后PM₁₀的物理化学特性,探讨了颗粒物可能的形成机理.结果表明,两台锅炉产生PM₁₀的质量粒径均呈双峰分布,峰值分别在0.1 μm和4 μm左右.粒径小于0.377 μm的颗粒可能为气化-凝结机理形成,超微米颗粒则可能是通过亚微米颗粒凝聚、聚结和矿物质熔融、破碎、聚结形成.亚微米颗粒中碱金属和碱土金属的氧化物或硫化物为其主要成分,而超微米颗粒中主要成分为难熔性氧化物.     

Ion Chromatographic Analysis of Ammonium Dinitramide–Oxidizer for Propellant and Pyrotechnic Applications

Analysis of ammonium dinitramide (ADN), the advance rocket propellant oxidizer, in pure form as well as in mixtures was carried out by ion chromatography (IC). The purity of ammonium dinitramide was directly determined by estimating the dinitramide ions and indirectly by estimating the impurities. Both methods gave results comparable with those determined by Differential Scanning Calorimetry and UV spectroscopy. The chemical composition of ADN in mixtures containing nitrate, chromate, chlorate, perchlorate, and thiocyanate ions was quantitatively estimated in the same solution without any interferences or prior separation of analyte ions. The newly developed ion chromatographic methods for the analysis of ADN are simple and fast with good accuracy and precision when compared to other analytical techniques. The IC methods are found to be highly suitable for quality control analysis of ADN containing compositions and for the online process monitoring of the formation of ADN in the reaction mixture.     

Alkali Metal Ions-Assisted Controllable Synthesis of Bismuth Ferrites by a Hydrothermal Method

Various bismuth ferrite compounds have been controllably synthesized by a hydrothermal method assisted by alkali metal ions (K⁺, Na⁺, and Li⁺). The as-prepared powders were characterized by X-ray powder diffraction, energy-dispersive spectroscopy, and transmission electron microscope. It was suggested that different alkali metal ions can result in the formation of rhombohedral BiFeO₃, orthorhombic Bi₂Fe₄O₉, and cubic Bi₁₂(Bi_0.5Fe_0.5)O_19.5, respectively.     

镍基金属氧化物活性阴极的制备和应用性能的研究

通过热分解法制备了不同掺杂金属配比的镍基金属氧化物活性阴极,考察了不同掺杂金属配比对活性阴极析氢过电位和长期稳定性的影响。在工业化试验条件下测试了活性阴极在高碱浓度中的抗Fe2+中毒和抗反向电流氧化的性能。用稳态极化法测定了镍基金属氧化物活性电极的极化曲线,通过X-射线衍射仪和扫描电镜分析解释了活性阴极在碱性溶液中的析氢行为,并探讨了在碱液中的电催化反应机制。以铁阴极为对照,采用热分解法制备的镍基金属氧化物活性阴极具有很好的电催化性能、长期使用稳定性、抗反向电流氧化作用和抗Fe2+中毒等性能。     

蠕虫孔状介孔Cr_2O_3的制备与表征

以硝酸铬为金属源,活性炭为硬模板,用真空辅助浸渍法制备了蠕虫孔状介孔Cr_2O_3,采用XRD、BET、TEM、TPR和UV-Vis对样品的物化性能进行了表征。结果表明,制备的介孔Cr_2O_3是具有六方晶型和比表面积高达112m^2·g^(-1)的晶体,平均孔径约6.5nm,与体相材料相比,介孔Cr_2O_3表现出良好的低温还原性能和吸光性能,这与其表面形貌和晶体结构有关。     

Gas phase hydrogenation of ortho-chloronitrobenzene (O-CNB) to ortho-chloroaniline (O-CAN) over unpromoted and alkali metal promoted-alumina supported palladium catalysts

A series of alkali metals (Li, Na, K and Cs) promoted alumina-supported palladium catalysts were prepared by a wet impregnation method and characterized by X-ray diffraction (XRD) and CO chemisorption measurements. The samples were tested for the gas phase hydrogenation of ortho-chloronitrobenzene (O-CNB) to ortho-chloroaniline (O-CAN) in a fixed-bed micro reactor at 250 °C under normal atmospheric pressure. The promoted-Pd/Al₂O₃ catalysts show higher conversion for O-CNB and the hydrogenation activity of O-CNB per site decreases with the increasing ionic radius of the alkali metal promoter ions. However, the selectivity for O-CAN remains more or less the same in both unpromoted and promoted catalysts and also irrespective of the nature of the alkali metal promoter ions used for promotion of alumina support. Despite, similar activity and selectivity observed between Li- and Na-promoted Pd/Al₂O₃ catalysts, the Na-promoted showed higher resistance for coke formation than a Li-promoted catalyst. The increase in the intrinsic activity of palladium site on alkali promotion has been attributed to the increase in hydrogenation activity over promoted catalysts.     

反应结晶制备硼氢化钾

针对Schlesinger法生产碱金属硼氢化物工艺存在的结晶母液循环成本较高和副产物累积导致产品质量降低等问题,设计开发了反应结晶制备硼氢化钾这一过程,用于处理生产过程中的结晶母液,以提高硼氢化物收率,同时生产出具备一定经济效益的硼氢化钾。采用了容量分析中的碘量法、光学显微镜分析技术和马尔文粒度分析仪、X射线粉末衍射仪等设备,考察了反应结晶过程各项因素对最终产品性质的影响。结果表明：控制反应物质的量之比为1.05~1.10,反应温度为50℃,降温速度10℃·h^-1,养晶温度0℃,可以得到符合行业标准的硼氢化钾产品。