DEA(TCNQ)2与TEA(TCNQ)2单晶上的STM热化学烧孔性能比较

利用STM隧道电流焦耳热诱导分解气化的热化学烧孔方法,对两种存储材料DEA(TCNQ)2和TEA(TCNQ)2的存储性能作了比较,DEA(TCNQ)2可以得到更高的存储密度、更大的信息孔深/孔径比,有更大的写入阈值电压.由此说明通过对存储材料的设计可以对存储系统的性能进行优化.     

DPA(TCNQ)2的烧孔阈值电压对脉宽的依赖关系

合成了一种新的二元电荷转移复合物DPA(TCNQ)2（二丙胺-7,7,8,8-四氰基对亚甲基苯醌)，并得到了其单晶ab面的STM高分辨图像，表面晶格常数与体相晶格常数的XRD数据完全一致.用STM成功地写入了5×5的信息点阵，并在5.1 μm×5.1 μm的面积上写入更大规模的信息点阵，写入的可靠性和稳定性都很高.实验发现，烧孔阈值电压强烈依赖于脉宽,这一现象不支持场致蒸发的机理.理论分析表明，它支持热化学烧孔的机理.     

STM热化学烧孔方式的信息存储——写入脉冲幅值和脉宽对信息点尺寸的影响

以扫描探针显微技术（SPM）为基础的超高密度信息存储是近年的研究的热点。前文^[1]利用STM针尖在TEA（TCNQ）2单晶上施加电压脉冲,得到了超高密度信息孔点阵,提出了热化学烧孔方式的STM信息存储技术,在STM扫描成像的过程中,隧道电流会流经样品,产生焦尔热。但通常扫描成像过程中的隧穿电流较小,焦耳热也较小,如能找到一种二元复合材料,一级分沸点较低,且与另一组分的结合能较弱,当足够大的电流流经时,所产生的焦耳热可能使低沸点的组分气化逸出,在样品表面形成纳米尺度的信息点。我们称这种存储模式为热化学烧孔方式的STM存储。基于这一思想,我们选择电荷转移复合物TEA（TCNQ）2作为存储材料,用STM写下了纳米微级的信息孔。本文通过改变写入电压脉冲的脉幅和脉宽,控制孔的大小,并对孔大小与脉冲电压的关系进行了理论推导和分析。     

镁铜合金储氢材料的制备及对高氯酸铵热分解过程的影响

采用置换-扩散法制备了镁铜合金储氢材料(Mg2Cu-H), 并对其结构进行了表征. 结果表明, Mg2Cu经过氢化得到的镁铜合金储氢材料不是单一晶相, 而是MgCu2和MgH2的混合物. 用热分析法(DSC)研究了镁铜合金储氢材料对固体火箭推进剂常用氧化剂——高氯酸铵(AP)热分解过程的影响. 结果表明, 镁铜合金储氢材料可以显著促进AP的热分解过程, 加快热分解速率, 降低高温热分解温度, 使DSC表观分解热明显增大. Mg2Cu-H对AP热分解过程的促进作用明显强于Mg2Cu. 随着加入量增加, 镁铜合金储氢材料对AP热分解的催化促进作用增强. 探讨了镁铜合金储氢材料促进AP热分解过程的作用机制.     

笼形倍半硅氧烷修饰的金纳米粒子对4-正戊基4'-氰基联苯液晶性能的影响

为有效降低液晶器件的开启电压,获得具有低功耗特性的液晶显示器件。本文采用巯基功能化的笼形倍半硅氧烷(POSS)作为修饰配体,硼氢化钠为还原剂,采用一步法还原氯金酸制备出粒径约为5 nm的金纳米粒子。将该金纳米粒子以不同质量分数掺杂到向列相液晶4-正戊基4'-氰基联苯(5CB)中,研究了其对液晶黏度、阈值电压、相变温度的影响。结果表明,POSS修饰的金纳米粒子可以使液晶材料5CB的黏度降低、阈值电压减小。该金纳米粒子的掺入,拓宽了液晶材料的相变温度范围。     

用STM针尖诱导热致气化模式的纳米级

以扫描探针显微镜(SPM)为基础的超高密度信息存储是近年来信息存储领域的热点研究之一.其基本原理是利用SPM针尖诱导存储介质表面形貌变化、导电性质改变、电荷分离等来记录信息.提出利用STM隧道电流的焦耳热效应诱导材料发生气化分解的热化学烧孔模式的STM存储新原理,并在电荷转移复合物TEA(TCNQ)2上成功地得到大面积信息孔阵列.空洞大小均一,最小直径约8nm.该存储模式有明显的优点:由于STM隧道电流波及范围很小,只要存储材料的导热性不是很好,则气化分解局限于非常小的范围,从原理上保证了存储的超高密度;写入可靠率非常高,达到99%以上;存储材料具有可设计性,易于优化材料的存储性能.     

聚芳醚醚酮的热老化寿命研究

本工作用热重法(TG)研究了聚芳醚醚酮(PEEK)在空气和氮气中的热分解反应过程;确定了PEEK在这两种气氛中的热分解反应模型均符合无规引发断裂模型;在空气中PEEK的热分解显示两个过程,由此计算其在空气中第一阶段的热分解和氮气中的热分解反应活化能分别为214.7kJ/mol和232.2kJ/mol;由热分解反应动力学参数推算出热老化寿命曲线,并讨论了实验条件对结果的影响,进而以失重5%作为材料寿终指标估算出PEEK在氮气和空气中使用10年的最高温度分别为307℃和274℃。     

1,2-亚乙基桥联咔唑和芳基噁二唑的双极传输材料的合成及光电性能研究

设计合成了三种1,2-亚乙基桥联咔唑和2,5-二芳基-1,3,4-噁二唑衍生物的双极传输材料,并通过核磁氢谱、碳谱、元素分析表征了它们的分子结构,研究了它们的紫外-可见吸收、光致发光、电化学和热稳定等性能.研究结果表明,这类双极传输材料具有咔唑和芳基噁二唑双功能基的紫外可见吸收和光致发光综合特性.热分解温度超过了340℃.与共轭基团桥联咔唑和芳基噁二唑的双极传输材料相比,HOMO/LUMO能级相应地提高,热稳定性能增强.     

微孔聚乳酸支架材料的热稳定性与动态热机械特性

采用无溶剂二氧化碳固态发泡技术,在2.5、3.5、4.0和5.0 MPa饱和压力下制备了泡孔孔径为350-20μm的聚乳酸支架材料.利用热重分析技术、动态热机械分析技术和扫描电子显微镜技术,测定了材料的起始分解温度、分解速率、储存/损耗模量和损耗因子等参数,并利用Kissinger、Ozawa-Doyle和Vyazovkin方程进行了热分解动力学计算,推算了氮气环境下材料的降解时间和使用寿命.结果表明,随着发泡压力的减小,支架材料的泡孔孔径增大,材料的柔韧性增强,表观活化能降低,降解时间缩短.     

热解条件对氮杂有序介孔炭材料电催化性能的影响

氧还原反应是燃料电池及金属空气电池中极其重要的电化学反应之一,贵金属铂基催化剂被认为是最有效的氧还原反应电催化剂.然而,贵金属铂的资源稀缺以及高成本问题阻碍了相关技术的大规模应用,探索发展廉价高效的贵金属替代型催化剂是推动燃料电池发展的根本解决方案.近年来,人们在非贵金属催化剂开发方面取得了显著进展,其中新型纳米结构掺杂炭材料研究尤为活跃.氮杂有序介孔炭材料由于其高比表面积和独特的孔结构,在燃料电池技术上具有广泛的应用前景.在氮杂有序介孔炭材料的制备过程中,热解条件对炭材料组成、结构及电催化性能有着重要影响.然而,目前尚未见对氮杂炭材料制备过程中热解条件的影响进行系统研究.
　　本文采用我们发展的蒸汽化-毛细管冷凝法,以SBA-15为硬模板浸渍前驱体吡咯,制备出具有高比表面积和独特孔结构的氮杂有序介孔炭材料,系统研究了热解条件(包括热解温度、热解时间和升温速率)对炭材料组成、结构及电催化性能的影响,采用N2吸附-脱附等温线、X射线光电子能谱(XPS)及Raman光谱等方法考察了氮杂有序介孔炭材料的结构和组成,采用循环伏安法与旋转环盘电极研究了其电化学行为与氧还原反应电催化活性及选择性.
　　N2吸附-脱附等温线显示,氮杂炭材料对应IV型吸附-脱附等温线,孔径主要分布在2–10 nm,表明所制材料具有介孔结构.随着热处理温度升高,氮杂有序介孔炭材料比表面积先增加而后降低,热处理时间的延长有利于比表面积增大,但升温速率对所制炭材料比表面积没有明显影响,当升温速率为30 oC/min,900 oC焙烧3 h时,氮杂有序介孔炭材料的比表面积达到最大值888 m2/g. XPS测试结果表明,随着热处理温度升高,氮杂有序介孔炭材料中含氮基团的分解进一步加深,使N含量逐渐降低.延长热处理时间亦然,而升温速率的改变对N含量无明显影响.在热处理温度较低时(600 oC),所得材料中N主要以吡咯氮和吡啶氮的形式存在;当温度达到800 oC以上,吡咯氮转化为吡啶氮和骨架氮,且主要以骨架氮形式存在,说明氮杂有序介孔炭材料的石墨化程度逐渐升高. Raman光谱结果显示,随着热处理温度升高, ID/IG逐渐降低,进一步印证了温度对石墨化程度的影响.
　　电化学测试结果表明,随着热处理温度升高,氮杂有序介孔炭材料的氧还原反应电催化活性逐渐升高,但是当热处理温度从900 oC升至1000 oC时,氧还原反应活性增加很小;升温速率与热处理时间对氧还原反应电催化活性的影响均不明显.与商品Pt/C催化剂相比,900 oC以上所制催化剂均表现出更优异的氧还原电催化活性与选择性.由此可见,热处理温度是决定碳源热化学行为的关键因素,进而决定炭材料表面组成与结构.电化学研究结果表明,800 oC以上进行热处理碳化,所生成石墨化微晶可有效促进电子传递,降低欧姆极化损失,同时,较高的处理温度可促进骨架氮掺杂,从而构建出高效氧还原反应活性位点.因此,氮杂型炭催化剂的组成、结构与电化学性能更多地受控于热处理过程中的热力学,而非热解动力学过程.     

Thermochemical hole burning on a series of N-substituted morpholinium 7,7,8,8-tetracyanoquinodimethane charge-transfer complexes for data storage

We demonstrate here the thermochemical hole burning (THB) effect on a series of N-substituted morpholinium 7,7,8,8-tetracyanoquinodimethane charge-transfer (C-T) complexes for ultra-high-density data storage. A correlation between the decomposition temperature of the charge-transfer complex and the threshold voltage of hole burning was observed: the higher the decomposition temperature, the larger the writing threshold value, suggesting the possibility of molecular design for optimizing the hole burning performance. The macroscopic decomposition properties of these charge-transfer complexes were studied by thermal gravimetry combined with mass spectrometry. Theoretical estimation of the temperature rise induced by scanning tunneling microscopy current heating was also conducted, which indicated that the maximum temperature certainly exceeds the decomposition temperatures of these C-T complexes. These observations are consistent with the thermochemical hole burning mechanism.     

Effect of ammonium oxalate/strontium carbonate on the burning rate characteristics of composite propellants

AP/HTPB based composite propellants with additives such as ammonium oxalate (AO), mixture of ammonium oxalate and strontium carbonate (SC) was investigated by burning rate, TG-DTG and FTIR experiments. The results show that the burning rates of these propellants are decreased significantly. TG-DTG experiments indicate that decomposition temperatures of AP with these additives are increased. Furthermore, the activation energy of the decomposition reaction of AP is also increased in the presence of AO or AO/SC. These results show that AO or AO/SC restrains the decomposition of AP. The burning rates of these propellants are decreased. The burning rate temperature sensitivity of AP/HTPB based propellants is reduced significantly by the addition of AO or AO/SC. But the effect of AO is less than that of AO/SC. AO/SC is better effect to reduce temperature sensitivity and at the same time, to reduce pressure exponent. The reduced heat release at the burning surface of AP/HTPB/AO is responsible for the reduced temperature sensitivity. Synergetic action is probably produced between AO and SC within AP/HTPB based propellants in the pressure range tested. This synergetic effect causes the heat release to reduce and the burning surface temperature to increase. Moreover, it makes the net exothermal reaction of condensed phase become little dependent on T ₀. Thus, the burning rate temperature sensitivity is reduced.     

Effect of iron-containing catalysts on thermal decomposition of cured GAP-AP propellants

The effects of various burning rate catalysts on thermal decomposition of cured glycidyl azide polymer (GAP)-ammonium perchlorate (AP) propellants have been studied by means of thermal analysis and a modified vacuum stability test (MVST). Four types of iron-containing catalysts examined in this paper are catocene, ferrocenecarboxaldehyde (FCA), ferrocene, and ferric oxide. Results of differential thermal analysis (DTA) and thermogravimetric analysis (TG) revealed that the catalysts play an important role in the decomposition of both AP and GAP. The peak decomposition temperature (T _m) of DTA curves and onset decomposition temperature (T _o) of TG patterns considerably shifted to a lower temperature as the concentration of catalysts increased in the propellants. The endothermic temperature of AP, however, is unaffected by the presence of burning rate catalysts in all cases. The activation energy of decomposition of the propellants in range of 80 to 120°C is determined, based on the MVST results.     

Thermochemical hole burning on a triethylammonium bis-7,7,8,8-tetracyanoquinodimethane charge-transfer complex using single-walled carbon nanotube scanning tunneling microscopy tips

The present article describes a thermochemical hole burning (THB) effect on a charge-transfer complex triethylammonium bis-7,7,8,8-tetracyanoquinodimethane (TEA(TCNQ)(2)) using single-walled carbon nanotube (SWNT) scanning tunneling microscopy (STM) tips, which demonstrates the possibility of optimizing the THB storage materials and the writing tips for ultrahigh-density data storage. TEA(TCNQ)(2) is proven to be a high-performance THB storage material, which gives deeper holes and larger hole depth-to-diameter ratio as compared to the previous materials dipropylammonium bis-7,7,8,8-tetracyanoquinodimethane and N-methyl-N-ethylmorpholinium bis-7,7,8,8-tetracyanoquinodimethane. Instead of conventional Pt/Ir STM tips, SWNT tips made by a unique chemical assembly technique we developed have been shown to be excellent writing tips for greatly decreasing the hole sizes and increasing the storage density. Possible reasons for the improvements on the storage performance were discussed.     

Thermal Analysis Studies on Isopropylnitrate

Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN₁. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol⁻¹. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPN_g. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g⁻¹ and -3.85±0.03 kJ g⁻¹, respectively from DSC and HFC measurements on IPN₁ samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol⁻¹ was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase. This revised version was published online in August 2006 with corrections to the Cover Date.     

Role of vapour oversaturation in the thermal decomposition of solids

Elementary thermochemical calculations show that in all cases of formation of solid product in the process of the congruent dissociative vaporization of reactants, the equilibrium partial pressure of the main product greatly exceeds its saturation vapour pressure, and therefore causes the appearance of vapour oversaturation. The oversaturation is responsible for the formation and growth of nuclei, their shape and position, the transfer of condensation energy to the reactant, the existence of induction and acceleration decomposition periods, the reaction localization, the epitaxial/topotaxy effects and the nanocrystal structure of the solid product. Variations in the energy transfer explain an increase of the molar enthalpy with temperature and the decelerating influence of melting on the rate of decomposition.     

Non-isothermal kinetic studies on thermal decomposition of energetic materials

Thermal stability and decomposition kinetics for two energetic materials, potassium nitroform (KNF) and 5-Nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO), were investigated to obtain information on their safety for handling, storage, and use. Differential scanning calorimetry (DSC) and simultaneous thermogravimetry-differential thermal analysis (TG-DTA) techniques have been used to study thermal behavior of these energetic compounds. The results of TG analysis revealed that the main thermal degradation for the KNF occurs during two temperature ranges of 270?C330 and 360?C430?°C. Meanwhile, NTO decomposes completely in temperature range of 250?C300 °C. TG-DTA analysis of KNF indicates that this energetic compound dehydrated (at about 108?°C) before its decomposition. However, NTO is thermally stable until its decomposition. The decomposition kinetic of energetic materials was studied by non-isothermal DSC under various heating rates. Kinetic parameters such as activation energy and frequency factor for thermal decomposition of energetic compounds were obtained via the methods proposed by ASTM E696 and Starink. Also, thermodynamic parameters correspond to the activation of thermal decomposition and critical ignition temperatures of the compounds were obtained.     

Thermal behavior of new oxidizer ammonium dinitramide

Ammonium dinitramide (ADN) is a promising new oxidizer for solid propellants because of its high oxygen balance and high energy content, and halogen-free combustion products. One of the characteristics needed for solid propellants is stability. Heat, light, and moisture are factors affecting stability during storage, manufacture, and use. For practical use of ADN as a solid propellant, clarification of the mechanism of decomposition by these factors is needed to be able to predict lifetime. This study focused on thermal decomposition of ADN. Exothermal behavior of ADN decomposition was measured by isothermal tests using high-sensitive calorimetry (TAM) and non-isothermal tests using differential scanning calorimetry (DSC). Based on these results, analysis of the decomposition kinetics was conducted. The activation energy determined by TAM tests was lower than that from DSC tests. Thus, the decomposition path in TAM tests was different from that in DSC tests. The amount of ADN decomposition predicted from TAM tests was closer to that found under real storage conditions than the amount of decomposition predicted from DSC tests. Non-isothermal tests may not be able to precisely predict the lifetime of materials with a decomposition mechanism that changes with temperature, such as ADN. The lifetime predicted from DSC results was much longer than that from TAM tests especially at low temperature. It is necessary to use isothermal tests to predict the long-term stability at low temperature.