Low Temperature Heat Capacities and Thermodynamic Properties of Zinc L-Threonate Zn(C_4H_7O_5)_2(s) by Adiabatic Calorimetry

Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.

SIGMAPLUG—A NEW TEMPERATURE INDICATOR FOR REMAINING LIFE ASSESSMENT OF HIGH TEMPERATURE COMPONENTS

Improved life assessment techniques will enable engineering components to be replaced before failure, thereby reducing the risk of industrial accidents as well as minimizing financial loss due to unscheduled outages. For components operating at high temperatures, temperature measurement is very important. In many situations, the environmental conditions are too hostile for conventional techniques to be used. Researchers over the world have been looking for new techniques for temperature measurement and one such device, called Feroplug, has been developed previously by the and coworkers. The Feroplug has been patented in USA, UK and Europe by the British Technology Group. The underlying principle of the Feroplug is based on the transformation of ferrite in some specially designed duplex stainless steels. This paper describes a new invention called Sigmaplug which is a new development of the Feroplug but using an entirely different physical principle. It was discovered that the sigma phase in Fe

UranyI Phosphonates with Multiple UranyI Coordination Geometries and Low Temperature Phase Transition

Main observation and conclusion Two new uranium(VI)phosphonate compounds,namely K_(8)[N(C_(2)H_(5))_(4)]_(2)(UO_(2))_(17)(H_(2)O)_(4)[CH_(2)(PO_(3))_(2)]_(8)[CH_(2)(PO_(3))(PO_(3)H)]_(4)·16(H_(2)O)(1)and[N(C_(2)H_(5))_(4)]_(4)(H_(3)O)_(2)(UO_(2))_(10)[CH_(2)(PO_(3))_(2)]_(5)[CH_(2)(PO_(3))(PO_(3)H)]_(2)·10H_(2)O(2),have been synthesized under mild hydro/solvothermal condition.The structural analysis of the two compounds reveals that they both contain all three typical coordination geometries of the U(VI)ions,including UO;tetragonal,UO,pentagonal,and UOg hexagonal bipyramids.Moreover,compound 1 displays a tempera-ture-induced single crystal to single crystal phase transformation as confirmed by the Single-crystal X-ray diffraction data collected at different temperatures.Temperature-dependent fluorescence spectra presented herein illustrate the perturbation of the electronic structure of uranyl centers.

Sintering characteristics, phase transitions, and microwave dielectric properties of low-firing [(Na_(0.5)Bi_(0.5))_(x)Bi_(1-x)](W_(x)V_(1-x))O_(4) solid solutionceramics

A series of high-k[(Na_(0.5)Bi_(0.5))_(x)Bi_(1-x)](W_(x)V_(1-x))O_(4)(abbreviated as NBWV(x value))solid solution ceramics with a scheelite-like structure are synthesized by a modified solid-state reaction method at the temperature range of 680-760 C.A monoclinic(0≤x<0.09)to tetragonal scheelite(0.09≤x≤1.0)structural phase transition is confirmed by X-ray difraction(XRD),Raman,and infrared(IR)analyses.The effect of structural deformation and order-disorder caused by Na^(+)/Bi^(3+)/W^(6+) complex substitution on microwave dielectric properties is investigated in deail.The compositional series possess a wide range of variable relative permittivity(er=24.8-80)and temperature coefficient of resonant frequency(TCF value,-271.9-188.9 ppm/℃).The maximum permittivity of 80 and a high Qxf value of~10,000 GHz are obtained near the phase boundary at x=0.09.Furthermore,the temperature-stable dielectric ceramics sintered at 680 C with excellent microwave dielectric properties of ε_(r)=80.7,Qxf=9400 GHz(at 4.1 GHz),and TCF value=-3.8 ppm/℃ are designed by mixing the components of x=0.07 and 0.08.In summary,similar sinterability and structural compatibility of scheelite-like solid solution systems make it potential for low-temperature co-fired ceramic(LTCC)applications.

CALORIMETRY AT VERY LOW TEMPERATURES——MAGNETIC PHASE TRANSITION OF THE FIVE-COORDINATED COPPER(Ⅱ) COMPLEX, Cu(L-ISOLEUCINE)_2(H_2O)

I. INTRODUCTION Calorimetry at very low temperatures is one of the useful tools for the investigation of magnetic properties of materials. Paramagnetic substances often exhibit

不同提取方法对井冈蜜柚皮精油组成与性质的影响

以井冈蜜柚皮精油(Jinggang pomelo peel essential oil,JPPEO)为研究对象,采用水蒸气蒸馏法、低温连续相变法两种方法进行提取,以精油得率为主要指标,研究了萃取温度、压力、时间等因素对井冈蜜柚皮精油得率的影响,并通过正交法进行低温连续相变法提取工艺优化,同时对精油的理化性质及化学组成进行分析。研究表明,低温连续相变提取井冈蜜柚皮精油(Low-temperature continuous phase transition extraction essential oil,L-JPPEO)的最佳工艺为:颗粒度30目,萃取温度55℃,萃取压力0.6 MPa,萃取时间60 min,解析温度70℃,此时精油得率为10.99‰,比水蒸气蒸馏法提取的精油(Hydro distillation essential oil,H-JPPEO)得率高出了2.88倍;理化性质实验结果表明,低温连续相变萃取的井冈蜜柚皮精油的不饱和脂肪酸含量较高,游离脂肪酸含量较低,酯类成分含量较低;傅里叶衰减全反射中红外光谱法(Fourier transform infrared spectroscopy,FTIR)鉴定出L-JPPEO和H-JPPEO含萜烯类化合物、醇类、酚类、醛类以及含羰基化合物。气相色谱-质谱联用法(Gas chromatography-mass spectrometry,GC-MS)从H-JPPEO、L-JPPEO样品中分别鉴定出23和32种化合物,其中两种精油都检测出的有15种物质,D-柠檬烯相对含量均最高,L-JPPEO中相对含量为4.75±0.16μg/mL,H-JPPEO中相对含量为640.93±44.47μg/mL;顶空气相色谱-离子迁移谱法(Headspace-gas chromatography-ion mobility spectrometry,HS-GC-IMS)从两种提取方法的精油均鉴定出71种化合物,与水蒸气蒸馏相比,低温连续相变萃取技术提取出较多的萜烯类(45.75%)、酮类(7.68%)及酯类(15.85%)、酸类(5.62%)成分。

超临界/密相CO_(2)管道泄漏压力响应及低温规律实验研究

为进一步了解超临界/密相CO_(2)在管道泄漏过程中的压力响应和温度变化,基于自行设计的高压CO_(2)管道泄漏实验装置,探讨压力响应、温降特性和相态变化的相互作用机理,以及低温分布规律。研究结果表明:19 mm口径纯CO_(2)的压降曲线有明显的2个阶段,且密相泄放存在明显的压力平台,N 2会明显提高泄放速率;相同截面上温度呈现“上热下冷”的分布特征,管道轴线方向,泄放端温降相对最严重;从相态变化角度看,超临界CO_(2)泄漏没有明显两相区,但对于密相而言,管道底部的CO_(2)会经历密相、液相、过热液相、气液两相、气相的相态转变过程。研究结果可为管道泄放安全运行以及规避断裂风险等方案设计提供参考。

700kW生物质真空相变锅炉的设计与性能实验

秸秆高温燃烧时,大量钾(K)元素以气相形式释放,造成秸秆灰渣失去肥性。将燃烧温度降低至700℃以下,有限控制钾(K)的逸出,提高秸秆灰的肥性,减轻烟管受热面结渣腐蚀。文章设计了一种生物质真空相变锅炉,真空相变换热可以提高换热效率,燃烧室和烟管都设置于真空水室之中,利用热管传热原理,真空水室中的水相变过程中快速带走燃烧产生的热量,从而降低燃烧温度。实验结果表明燃烧室内温度可以降低到700℃左右。

Crystal structure and thermochemical properties of bis(1-octylammonium) tetrachlorochromate phase change materials

A new crystalline complex （C8H17NH3）2CdCI4（s） （abbreviated as CsCd（s）） is synthesized by liquid phase reaction. The crystal structure and composition of the complex are determined by single crystal X-ray diffraction, chemical analysis, and elementary analysis. It is triclinic, the space group is P-1 and Z = 2. The lattice potential energy of the title complex is calculated to be UpoT （CsCd（s））=978.83 kJ.mol^-1 from crystallographic data. Low-temperature heat capacities of the complex are measured by using a precision automatic adiabatic calorimeter over a temperature range from 78 K to 384 K. The temperature, molar enthalpy, and entropy of the phase transition for the complex are determined to be 307.3±0.15 K, 10.15±0.23 kJ.mol^-1, and 33.054-0.78 J.K^-1.mol^-1 respectively for the endothermic peak. Two polynomial equations of the heat capacities each as a function of temperature are fitted by using the leastsquare method. Smoothed heat capacity and thermodynamic functions of the complex are calculated based on the fitted polynomials.

Raman and luminescence studies on phase transition of EuNbO_4 under high pressure

Raman and luminescence studies on the phase transition of europium orthoniobates （EuNbO4） under high pressure were performed. The pressure dependent Raman spectra revealed that an irreversible phase transition from monoclinic phase to M＇-fergusonite phase of EuNbO4 occurred at 7.3 GPa, and the two phases coexisted over a pressure range from 7.3 to 13.7 GPa. An obvious discontinuity on luminescence intensity ratio between 5D0 →7F2 and 5D0→7F1 transitions was observed with increasing pressure, in- dicating also that a phase transition occurred at 7.3 GPa, which was in agreement with the high pressure Raman spectra data. Mean- while, the Raman and luminescence spectra in the temperature range of 20--300 K showed the structure stability at low temperatures.

Low-melting mixture solvents:extension of deep eutectic solvents and ionic liquids for broadening green solvents and green chemistry

Green solvents such as water and ionic liquids(ILs)are pillars of the great mansion of green chemistry and green processing.Initially proposed as a new family of ILs,deep eutectic solvents(DESs)have received fast development in the past two decades.In this contribution,DESs are reviewed critically and the concept is extended to lowmelting mixture solvents(Lo MMSs),which cover all kinds of materials including ionic compounds,molecular compounds,and metals.Six classes of Lo MMSs are proposed as the new classification system and examples are given.Finally,several thermodynamic issues concerning Lo MMSs are discussed.Two new concepts,robustness of Lo MMSs and high-entropy Lo MMSs,are proposed.

Exciting News from Indentations onto Silicon, Copper, and Tungsten

Indentations onto crystalline silicon and copper with various indenter geometries, loading forces at room temperature belong to the widest interests in the field, because of the physical detection of structural phase transitions. By using the mathematically deduced FNh3/2 relation for conical and pyramidal indentations we have a toolbox for deciding between faked and experimental loading curves. Four printed silicon indentation loading curves (labelled with 292 K, 260 K, 240 K and 210 K) proved to be faked and not experimental. This is problematic for the AI (artificial intelligence) that will probably not be able to sort faked data out by itself but must be told to do so. High risks arise, when published faked indentation reports remain unidentified and unreported for the mechanics engineers by reading, or via AI. For example, when AI recommends a faked quality such as “no phase changes” of a technical material that is therefore used, it might break down due to an actually present low force, low transition energy phase-change. This paper thus installed a tool box for the distinction of experimental and faked loading curves of indentations. We found experimental and faked loading curves of the same research group with overall 14 authoring co-workers in three publications where valid and faked ones were next to each other and I can thus only report on the experimental ones. The comparison of Si and Cu with W at 20-fold higher physical hardness shows its enormous influence to the energies of phase transition and of their transition energies. Thus, the commonly preferred ISO14577-ASTM hardness values HISO (these violate the energy law and are simulated!) leads to almost blind characterization and use of mechanically stressed technical materials (e.g. airplanes, windmills, bridges, etc). The reasons are carefully detected and reported to disprove that the coincidence or very close coincidence of all of the published loading curves from 150 K to 298 K are constructed but not experimental. A tool-box for distinction of experimental from faked indentation loading curves (simulations must be indicated) is established in view of protecting the AI from faked data, which it might not be able by itself to sort them out, so that technical materials with wrongly attributed mechanical properties might lead to catastrophic accidents such as all of us know of. There is also the risk that false theories might lead to discourage the design of important research projects or for not getting them granted. This might for example hamper or ill-fame new low temperature indentation projects. The various hints for identifying faked claims are thus presented in great detail. The low-temperature instrumental indentations onto silicon have been faked in two consecutive publications and their reporting in the third one, so that these are not available for the calculation of activation energies. Conversely, the same research group published an indentation loading curve of copper as taken at 150 K that could be tested for its validity with the therefore created tools of validity tests. The physical algebraic calculations provided the epochal detection of two highly exothermic phase transitions of copper that created two polymorphs with negative standard energy content. This is world-wide the second case and the first one far above the 77 K of liquid nitrogen. Its existence poses completely new thoughts for physics chemistry and perhaps techniques but all of them are open and unprepared for our comprehension. The first chemical reactions might be in-situ photolysis and the phase transitions can be calculated from experimental curves. But several further reported low temperature indentation loading curves of silicon were tested for their experimental reality. And the results are compared to new analyses with genuine room temperature results. A lot is to be learned from the differences at room and low temperature.

纳米铁酸盐的制备研究 低温催化相转化法合成纳米级铁酸锌及表征

以ＺｎＳＯ４·７Ｈ２Ｏ和ＦｅＣｌ３·６Ｈ２Ｏ为原料，在微量相转化催化剂存在下，利用沸腾回流的液相法制备了纳米铁酸锌微晶．当反应物总浓度高达１．２ｍｏｌ·Ｌ－１时，仍可获得粒径＜２０ｎｍ均匀粒子．研究了初始ｐＨ值对产物组成的影响．使用ＸＲＤ、ＴＥＭ、ＩＲ及磁强仪对产物进行了表征，并测定了所得产物的密度及比表面．

裂隙岩体冻融损伤关键问题及研究状况

工程岩体冻融损伤问题是寒区常见的工程难题,其主要诱因是岩体中水分的冻胀融缩作用。目前国内外学者关于冻岩问题的主要研究内容可大体归纳为冻岩物理力学性质、相变过程、低温多场(THM)耦合、冻融损伤模型及数值分析等4个大方面。几十年来,国内外学者通过理论分析、数值模拟、现场及室内试验等多种途径对冻岩问题展开研究,取得了丰硕的成果,但目前对冻岩问题的研究远未成熟,很多研究尚停留在试验探索阶段。要真正意义上揭示冻岩损伤机制,应以水冰相变为切入点,立足细观尺度,充分考虑冻胀融缩作用与裂隙扩展的相互影响,进而拓展至冻融作用对岩体裂隙网络发展的影响。

低温烧结钒和钨掺杂钛酸锌介电陶瓷的相转变

采用化学法结合传统的氧化物固相烧结法制备钛酸锌陶瓷。研究了原料形态和掺杂V2O5和WO3对钛酸锌陶瓷相稳定性、显微组织以及低温烧结行为的影响,讨论了相转变机制和低温烧结机制。研究表明:以V2O5和WO3作为烧结助剂降低陶瓷的烧结温度,钛酸锌陶瓷的低温烧结行为对所选取的原料极为敏感,TiO2的活性对陶瓷低温烧结行为的影响大于ZnO。V2O5和WO3的掺入使钛酸锌陶瓷的烧结温度降至900℃以下,但同时降低了六方相ZnTiO3的分解温度;V2O5和WO3掺杂具有不同的烧结机制,前者主要是液相烧结机制,后者主要是固相反应烧结机制。掺杂导致的相分解和生成的异相降低了陶瓷的介电性能。

陈皮挥发油的低温连续相变萃取及特性分析

陈皮作为传统中药材,其所含挥发油具有祛痰、平喘等多种药理作用。本研究采用低温连续相变萃取技术从陈皮中提取挥发油,探讨了原料颗粒度、萃取时间、萃取压力、萃取温度和和解析温度对提取率的影响,并通过L9(34)正交试验优化萃取工艺对挥发油提取率的影响。同时对陈皮挥发油理化性质和脂肪酸组成进行了分析。结果表明,低温连续相变萃取陈皮挥发油的最佳工艺条件为:原料颗粒度40目,萃取时间60 min,萃取压力0.6 MPa,萃取温度30℃,解析温度70℃,在此条件下陈皮挥发油的提取率为3.31%。低温连续相变萃取陈皮挥发油呈黄色至红棕色半固体膏状物,内含10.6%多甲氧基黄酮类物质,碘值为122.4 g I/100 g,酸价为73.8 mg KOH/g,过氧化值为0.1 g/100 g。经GC-MS分析发现,陈皮挥发油主要脂肪酸组成为亚油酸(30.01%),十八碳-9-烯酸(25.43%),亚麻酸(16.32%)和硬脂酸(4.56%)。

过渡金属对选择性催化还原脱硝CeO_2@TiO_2催化剂低温活性的促进作用

采用过渡金属M(M=Mn、Co、Fe和Cu)掺杂改性自发沉积策略制备的非晶态CeO_2@TiO_2催化剂,考察M-CeO_2@TiO_2选择性催化还原NO_x的低温活性,并通过XRD、TEM、N2吸附-脱附、H2-TPR、NH3-TPD及in-situ FT-IR等表征手段研究M-CeO_2@TiO_2的结构、表面性质以及低温NH3-SCR反应过程。结果表明,M-CeO_2@TiO_2具有更优异的低温氧化还原能力以及更多的表面酸量,且Cu掺杂对CeO_2@TiO_2选择性催化还原NO_x低温活性具有最为显著的促进作用。Cu-CeO_2@TiO_2催化剂在低温NH3-SCR反应过程中同时存在E-R机理和L-H机理,但是由于"快速SCR"使得L-H机理反应起关键作用。

低温连续相变萃取蓝圆鲹鱼油及其脂肪酸组成分析

采用新型萃取技术——低温连续相变萃取技术提取蓝圆鲹鱼油,考察物料水分含量、萃取温度、压力、时间、解析温度等因素对蓝圆鲹鱼油得率的影响,通过响应面设计确定最佳提取工艺条件,并对蓝圆鲹鱼油的理化性质和脂肪酸组成进行了分析。研究结果表明,低温连续相变萃取蓝圆鲹鱼油的最佳工艺为:物料水分含量11%,萃取温度52℃,萃取时间62 min,萃取压力0.6 MPa,解析温度为65℃,此工艺条件下鱼油得率为21.56%。鱼油外观为黄色至红棕色,有较淡的鱼腥味,其理化指标达到了粗鱼油标准SC/T3502-2000的一级要求。气相色谱-质谱法(GC-MS)分析鉴定出20种脂肪酸,多不饱和脂肪酸为59.57%,其中二十碳五烯酸(EPA)与二十二碳六烯酸(DHA)占总脂肪酸含量的24.62%。低温连续相变萃取技术应用于鱼油生产,具有萃取效率高、萃取温度低、对鱼油成分无破坏等特点,显示出良好的经济效益及应用前景。

WO_3-B_2O_3复合掺杂钛酸锌陶瓷的低温烧结和相转变

采用传统氧化物混合法结合半化学工艺制备了钛酸锌陶瓷,研究了WO3-B2O3复合掺杂对陶瓷低温烧结行为、低烧机制和相转变的影响。研究结果表明:WO3-B2O3掺杂将陶瓷烧结温度从1100℃降至900℃;WO3和B2O3的降温机制不同,前者主要是固相反应烧结机制,而后者应为液相烧结机制;WO3促进了六方相ZnTiO3的分解,对其原因进行了探讨;测试了不同频段下试样的介电性能,发现不同频段下,极化机制不同。

10Ni5CrMoV钢焊接残余应力研究

焊接结构中较大的焊接残余应力的存在往往导致焊接结构性能恶化。而一般来说,钢的屈服强度越高则往往导致其焊接结构中的焊接残余拉应力越大。本文针对屈服强度近800MPa的高强钢10Ni5CrMoV钢平板堆焊试样的焊接残余应力进行了研究。结果表明,焊接各区域并未出现较大值的焊接残余拉应力,甚至出现压应力。分析其原因,是焊缝与母材的线膨胀系数匹配、焊缝材料在焊接冷却过程中的低温相变所致。