邻苯二甲酸氢铵NH4(C8H5O4)(s)的低温热容和热化学研究

选择分析纯邻苯二甲酸和浓氨水为反应物,合成了邻苯二甲酸氢铵.利用元素分析、FTIR和X-射线粉末衍射技术表征了它的组成和结构.用精密自动绝热热量计测定了它在78～400 K温区的摩尔热容,将该温区的摩尔热容实验值用最小二乘法拟合,得到摩尔热容(Cp,m)随折合温度(X)变化的多项式方程,利用此方程计算出该温区内每隔5 K的舒平热容值和相对于298.15K的各种热力学函数值.另外,依据Hess定律,通过设计合理的热化学循环,利用等温环境溶解-反应热量计分别测定所设计反应的反应物和产物在所选溶剂中的溶解焓,得到该反应的反应焓为△rHθm=(1.787±0.514)kJ·mol-1.最后,利用此反应焓和反应中其他物质的热力学数据计算出邻苯二甲酸氢铵的标准摩尔生成焓为:△fHθm[NH4(C8H5O4),s]=-(912.953±0.628)kJ·mol-1.     

Correlation between properties of a solid sample and laser-induced plasma parameters

To investigate the influence of mechanical properties of a solid sample on the laser-induced plasma parameters (temperature and mass ablated) a number of aluminum–lithium alloys and lithium ferrites with different microstructure and composition have been studied. The specific approach to estimate excitation temperature for low-resolution emission spectra has been developed. The main limitations of this approach were discussed on the basis of comparison with the energy width of several multiplets. Overall uncertainties for temperature calculation were evaluated by taking into account the accuracy of Einstein's coefficients and errors of the proposed multiplets method. The temporal evolution of laser plasma during the evaporation of these materials was studied. Extremely high value of the Li I excitation temperature has been estimated to be T > 10⁵ K for the annealed ferrite ablation, in contrast to the temperature T  1.5 · 10⁴ K for non-annealed ferrite. Only for ablation of annealed ferrite the Li II emission line at 548.4 nm was observed. It means that this laser-induced plasma was the hottest. In the case of alloys, the temperature calculated by using Li I transitions was proportional to the microhardness of the solid samples. The negative correlation between crater volume/opto-acoustic signal and alloy microhardness was observed. At the first pulses the mechanical properties of the alloys didn't correlate with the ablated mass, while the maximal correlation coefficients were observed after ablation by 10 or 50 consequent laser pulses.     

Synthesis of nanosized silicon particles by a rapid metathesis reaction

A solid-state rapid metathesis reaction was performed in a bed of sodium silicofluoride (Na₂SiF₆) and sodium azide (NaN₃) powders diluted with sodium fluoride (NaF), to produce silicon nanoparticles. After a local ignition of Na₂SiF₆+4NaN₃+kNaF mixture (here k is mole number of NaF), the reaction proceeded in a self-sustaining combustion mode developing high temperatures (950–1000 °C) on very short time scales (a few seconds). Silicon nanoparticles prepared by the combustion process was easily separated from the salt byproducts by simple washing with distilled water. The structural and morphological studies on the nanoparticles were carried out using X-ray diffractometer (XRD) and field emission scanning electron microscope (FESEM). The mean size of silicon particles calculated from the FESEM image was about 37.75 nm. FESEM analysis also shows that the final purified product contains a noticeable amount of silicon fibers, dendrites and blocks, along with nanoparticles. The mechanism of Si nanostructures formation is discussed and a simple model for interpretation of experimental results is proposed.     

催化剂低温NH3选择催化还原NO的研究

研究了碳纳米管担载的五氧化二钒（V₂O₅/CNTs）催化剂上NO低温选择催化还原反应（SCR）。与活性炭载体的催化剂作了对比,结果显示,在负载低含量V₂O₅时碳纳米管较活性炭显示了更好的催化能力,而且在SO₂存在下,催化性能有更大幅度的提高。暂态反应实验显示,V₂O₅/CNTs 催化剂上NO选择催化还原反应遵循Eley Rideal机理,即反应发生于吸附态的NH₃和气相或弱吸附的NO之间。     

Influence of chain architecture on phase behaviour of styrene-(styrene/butadiene)-styrene triblock copolymers and their binary blends

The phase behaviour of symmetric (LN4) and asymmetric (LN3) triblock copolymers based on styrene-b-(styrene-co-butadiene)-b-styrene (S-SB-S) and their blends have been studied using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and were correlated with rheological properties. A direct control over the final morphology and segregation strength for the block copolymer blends was achieved by blending of LN3 and LN4. The interaction parameter (χ) for LN4 is extracted by fitting the SAXS patterns at temperatures well above the ODT in consistency with Leibler mean-field structure-function for ABA triblock copolymers. A weak temperature dependency of χ has been observed which revealed that the phase behaviour in LN4 is mainly controlled by the entropic term. In the low frequency regime a non-terminal flow behaviour was observed in LN3 revealing the persistence of ordered structure within the experimental temperature range whereas a terminal flow behaviour with composition fluctuation was observed in LN4. G′ vs. G″ plots indicated a solid-like elastic melt behaviour for LN3 whereas presence of ODT over a broad temperature range was observed for LN4. ODT is observed to increase non-linearly with increase in LN3 content in the blends. ODT behaviour of the blends further reveals that the blends shift from weak-segregation to intermediate-segregation strength with the increase in LN3 content. The improvement in the state of ordering along with the change in morphology with the increase of LN3 content is attributed to co-surfactant effect between the PS end-blocks of LN3 and LN4 inside PS-rich phase.     

High temperature NMR approach of mixtures of rare earth and alkali fluorides: An insight into the local structure

In situ high temperature nuclear magnetic resonance in molten fluoride mixtures gives some structural picture of the complexes existing in the melt, i.e. of their nature and relative proportion. Thanks to the development of a laser heating system associated with a close crucible in boron nitride, we can describe experimentally the evolution of these complexes from the anions and the cations point of view. By ¹⁹F NMR, we have shown the existence of three kinds of fluorine atoms depending on the composition: free fluorine like in pure LiF (non-bonded), bridging fluorine in melts rich in LnF₃ in addition with terminal fluorine singly bonded to one rare earth. Data obtained by NMR spectroscopy are also combined with EXAFS measurements, again thanks to a specific development of the sample holder adapted with molten fluorides and high temperature. This study is a part of our systematic investigation of the different Alk-LnF₃ systems by NMR and EXAFS spectroscopy.     

Chemical interaction in the B-BN system at high pressures and temperatures.: Synthesis of novel boron subnitrides

Chemical interaction and phase transformations in the B-BN system have been in situ studied by X-ray diffraction with synchrotron radiation at pressures up to 5.3 GPa and temperatures up to 2800 K using multianvil press. New rhombohedral boron subnitride B₁₃N₂ has been synthesized by crystallization from the B-BN melt at 5 GPa. The structure of B₁₃N₂ belongs to the R-3m space group (a=5.4455(2) Å, c=12.2649(9) Å) and represents a new structural type. The subnitride is an individual compound and not a solid solution, in contrast to boron carbide. Besides, the formation of two other boron-rich B-N phases denoted as “B₆N” and “B₅₀N₂” has been observed. Their structures seem to be much more sophisticated and have not been even resolved to present time.     

Modelling spur chemistry for alkaline and acidic water at high temperatures

The effect of pH and associated ionic strength on the primary yields in the radiolysis of pressurised water has been assessed by diffusion-kinetic calculations for temperatures in the range 100–300°C. Account has been taken for ionic strength I up to 0.1 mol kg⁻¹, assuming that the counter ions of H⁺ in acid solutions and of OH⁻ in base solutions have unit charge. In acid solutions, the H⁺ ions react with e⁻ _aq. The decrease in G(e⁻ _aq) and the increase in G(H) with decreasing pH becomes substantial for [H⁺] ≥ 1 × 10⁻⁴ m, but the primary yields of oxidising species are almost constant. In alkaline solutions, the OH⁻ anions affect the spur chemistry of radiation-generated protons and hydroxyl radicals for [OH⁻] ≥ 1 × 10⁻⁴ m. The scavenging of H atoms and hydrogen peroxide becomes significant for [OH⁻] ≥ 1 × 10⁻² m. The total yields G(OH) + G(O⁻) and G(H₂O₂) + G(HO₂ ⁻) are independent of base concentration below 0.01 m. In more alkaline solutions, G(OH) + G(O⁻) increases, whereas G(H₂O₂) + G(HO₂ ⁻) decreases with increasing [OH⁻]. Calculations showed the substantial yield of the reaction O⁻ + e⁻ _aq in 0.1 m base solution. Spur chemistry in alkaline hydrogenated water is not affected by the presence of H₂ if less than 0.001 m of hydrogen is added.     

Thermal characterization of piezoelectric and non-piezoelectric Lead Meta-Niobate

Powerful tools like Differential Scanning Calorimetry (DSC) and DTA seem to be under-utilized for the emerging materials for high temperature piezoelectric sensors, while thermal aspects of such piezoelectric phase change are also of theoretical interest. Curie temperature of Lead Meta-Niobate (PbNb₂O₆ or PN) is 570 °C, much higher than that for widely used lead zirconate titanate, making PN potentially more attractive at high temperatures. However, the only specific heat measurement for PN appears to be the 2–25 K study by Lawless, leaving the Curie temperature region unexplored. For PN, piezoelectricity is possible for the meta-stable orthorhombic structure only. So, we prepared pure phase orthorhombic PN by quenching (Q) and the rhombohedral PN by slow-cooling (S). We report for the first time, to our knowledge, DSC across the Curie temperature for Q and S types of PN. We find clear and interesting DSC signals at the Curie temperature in heating and cooling graphs for quenched (Q) PbNb₂O₆ only and none for the slow-cooled (S) PbNb₂O₆.     

热处理条件对R-PET/LLDPE-g-MA共混物中PET玻璃化转变行为的影响

对回收聚对苯二甲酸乙二酯(R-PET)/LLDPE-g-MA马来酸酐改性的线性低密度聚乙烯共混物进行不同条件的热处理, 采用差示扫描量热仪(DSC)研究共混物基体PET的玻璃化转变行为. 结果表明, 当热处理温度低于PET的玻璃化转变温度(Tg)时, PET的玻璃化转变区域出现热焓松弛现象. 随着热处理温度的增加, PET的Tg逐渐升高; 在50~70 ℃下热处理48 h后, PET的Tg逐渐稳定. 当热处理温度高于PET的Tg而低于100 ℃时, PET的玻璃化转变区域出现2个热流转变, FTIR分析表明, PET分子构象开始发生变化. 当热处理温度为100 ℃时, DSC曲线上PET的玻璃化转变消失, PET的结晶度明显增加, 说明PET开始冷结晶的温度在90~100 ℃之间.