Column Selectivity Programming and Fast Temperature Programming for High-Speed GC Analysis of Purgeable Organic Compounds

High-speed gas chromatograms are obtained by the use of relatively short lengths of capillary column operated at relatively large carrier gas flow rates. This approach is difficult for more complex mixtures because of the reduced peak capacity available with shorter columns. A solution to this problem is the use of tunable column ensembles consisting of the series (tandem) combination of a polar and a nonpolar column. By adjusting the pressure at the junction point between the columns, the selectivity of the ensemble can be adjusted within the limits imposed by the individual columns. For mixtures representing a relatively large boiling point range and containing more than ～20 components, high-speed, isothermal separations are less effective. These limitations are significantly reduced by combining fast temperature programming with selectivity programming. Selectivity programming is obtained by changing the pressure at the column junction point one or more times during the course of an analysis. In the work described here, the column ensemble temperature and the junction pressure are initially set to give a high-quality separation of the earliest eluting components. After these components have eluted, a linear temperature ramp of ～35 °C/min is initiated. As the temperature increases, the pressure is adjusted to change the selectivity and thus facilitate the separation of groups of components as they migrate through the column ensemble. Using this approach, a mixture of 30 purgeable organic compounds is separated in less than 2.5 min.     

Temperature Programming for High-Speed GC

Fast temperature programming (20-50 °C/min) is used with relatively short separation columns to achieve high-speed separations of mixtures covering a wide boiling point range. A cryofocusing inlet is used to obtain narrow injection plugs. High-speed temperature-programmed chromatograms are evaluated by considering local peak capacity as a function of carbon number and boiling point for the normal alkanes in the range C(8)-C(19). The peak capacity generation rate (peaks per second) as a function of carbon number and the total cumulative peak capacity as a function of time are also considered for various column lengths and carrier gas flow rates. Column lengths in the range 3.6-25.4 m and average carrier gas velocity values in the range 50-200 cm/s are considered. For a 6.8-m-long, 0.25-mm-i.d. column operated at an average carrier gas velocity of about 100 cm/s and using a nominal programming rate of 50 °C/min, C(19) elutes in 178 s with a total peak capacity of 168 peaks. If the programming rate is reduced to 20 °C/min, the C(19) elution time more than doubles but the total peak capacity increases by only 20%. For a 25.4-m-long column using a nominal 50 °C/min programming rate, the C(19) retention time is 262 s with a peak capacity of 279 peaks. The use of average carrier gas flow rates greater than about 100 cm/s, which is common in isothermal high-speed GC, results in a considerable loss in total peak capacity with remarkably little reduction in analysis time.     

Tunable Spectrum Selectivity for Multiphoton Absorption with Enhanced Visible Light Trapping in ZnO Nanorods

Observation of visible light trapping in zinc oxide (ZnO) nanorods (NRs) correlated to the optical and photoelectrochemical properties is reported. In this study, ZnO NR diameter and c‐axis length respond primarily at two different regions, UV and visible light, respectively. ZnO NR diameter exhibits UV absorption where large ZnO NR diameter area increases light absorption ability leading to high efficient electron–hole pair separation. On the other hand, ZnO NR c‐axis length has a dominant effect in visible light resulting from a multiphoton absorption mechanism due to light reflection and trapping behavior in the free space between adjacent ZnO NRs. Furthermore, oxygen vacancies and defects in ZnO NRs are associated with the broad visible emission band of different energy levels also highlighting the possibility of the multiphoton absorption mechanism. It is demonstrated that the minimum average of ZnO NR c‐axis length must satisfy the linear regression model of Z _p,min = 6.31d to initiate the multiphoton absorption mechanism under visible light. This work indicates the broadening of absorption spectrum from UV to visible light region by incorporating a controllable diameter and c‐axis length on vertically aligned ZnO NRs, which is important in optimizing the design and functionality of electronic devices based on light absorption mechanism.     

Optimization of the Time for a Chromatograph Thermostat to Reach a Specified Temperature

Measurement Techniques - The problems of ensuring the stability of the temperature of a chromatographic experiment carried out using a serial gas chromatograph LGKh-3000 are considered. The...     

Melting Temperature and Change of Lamellar Thickness with Time for Bulk Polyethylene

The melting temperature of linear polyethylene has been obtained as a function of the time and temperature of crystallization. Recrystallization was minimized by a special melting procedure. By interpreting the melting points as characteristic of a given lamellar thickness, it was found that the thickness of crystals of appreciable age increased linearly with the logarithm of their time of existence. The lowest melting (i.e., thinnest) lamellae in a given specimen may be assumed to have either existed for only a short period of time, or to have been impeded in their growth in the chain direction, and they were found to have an estimated thickness close to that predicted by recent kinetic theories of polymer crystal growth with chain folding.     

基于时间窗和多仓温控的生鲜商品配送车辆路径优化问题

目的 针对当前生鲜商品配送效率低和成本高等问题,采用车仓温度可控的多仓车辆作为配送装备,并结合时间窗等约束,研究基于时间窗和多仓温控的生鲜商品配送车辆路径优化问题。方法 建立最小化物流运营成本和车辆使用数量的双目标模型,然后设计基于Clarke-Wright节约算法的非支配排序遗传算法（CW-NSGA-Ⅱ）求解该模型。利用CW节约算法生成初始配送路径,以提高初始解的质量,并设计精英迭代策略,以提高算法的寻优性能。结果 基于改进的Solomon算例,将文中所提算法与多目标粒子群算法、多目标蚁群算法、多目标遗传算法进行了对比,验证了CW-NSGA-Ⅱ算法的求解性能。结合实例,对多仓车辆使用数量、温控成本和运营成本等指标进行对比分析,结果表明,经优化后多仓车辆使用数量减少了35.7%,温控成本减少了39.2%,物流运营总成本减少了47.7%。结论 文中所提模型和算法能够有效优化配送路径,降低运营成本,为构建高效率、低成本的生鲜配送网络提供了理论支持和决策参考。     

3D Printing Hierarchical Silver Nanowire Aerogel with Highly Compressive Resilience and Tensile Elongation through Tunable Poisson's Ratio

Metallic aerogels have attracted intense attention due to their superior properties, such as high electrical conductivity, ultralow densities, and large specific surface area. The preparation of metal aerogels with high efficiency and controllability remains challenge. A 3D freeze assembling printing technique integrated with drop‐on‐demand inkjet printing and freeze casting are proposed for metallic aerogels preparation. This technique enables tailoring both the macrostructure and microstructure of silver nanowire aerogels (SNWAs) by integrating programmable 3D printing and freeze casting, respectively. The density of the printed SNWAs is controllable, which can be down to 1.3 mg cm^?3. The ultralight SNWAs reach high electrical conductivity of 1.3 S cm^?1 and exhibit excellent compressive resilience under 50% compressive strain. Remarkably, the printing methodology also enables tuning aerogel architectures with designed Poisson's ratio (from negative to positive). Moreover, these aerogel architechtures with tunable Poisson's ratio present highly electromechanical stability under high compressive and tensile strain (both strain up to 20% with fully recovery).     

柔性染料敏化太阳电池光阳极的优化及叠层电池的初步研究

在前期对冷等静压制备柔性染料敏化太阳电池(DSC)研究的基础上, 开展了浆料的优化及叠层DSC的研究。首先利用水热法处理由小颗粒P25调配的浆料, 发现处理后浆料的稳定性及DSC的效率得到了大幅提高。在P25浆料中加入不同比例200 nm TiO₂大颗粒提高光散射, 当P25与200 nm TiO₂比例为4:1时, DSC获得最高光电转换效率3.11%。在此基础上, 尝试用N719和N749双层染料敏化, 发现双层染料敏化后电池的效率介于N719和N749单独敏化的电池效率, 这可能是由于光阳极变厚不利于电子传输以及染料相互接触影响染料纯度, 光阳极厚度及电池结构有待于进一步优化。     

Selectivity enhancement for high-speed GC analysis of volatile organic compounds with portable instruments designed for vacuum-outlet and atmospheric-pressure inlet operation using air as the carrier gas.

A tandem ensemble of two 4.5-m-long x 0.25-mm-i.d. capillary columns with the first using a 0.50-microm film of nonpolar dimethyl polysiloxane and the second using a 0.25-microm film of polar trifluoropropylmethyl polysiloxane is operated with atmospheric pressure air as the carrier gas and an outlet pressure of 50.5 kPa established using a small vacuum pump. A thicker stationary-phase film is used in the first column to increase retention for very volatile compounds. This significantly increases the resolution of these compounds. The thicker film in the first (nonpolar) column decreases the polarity of the tandem column ensemble and, thus, changes its selectivity. A low-dead-volume valve, connected between the column junction point and a source of atmospheric pressure air, is used to obtain pulsed modulation of the carrier gas flow through the column ensemble. When the valve is open, the ensemble inlet pressure and the junction-point pressure are nearly the same, and carrier gas flow nearly stops in the first column, and flow in the second column increases. Enhanced resolution of a component pair that is separated by the first column but coelutes from the column ensemble can be obtained if the valve is opened for a few seconds after one of the components has crossed the junction and is in the second column, but the other component is still in the first column. A sequence of appropriately timed pulses is used to obtain enhanced resolution of several pairs of components that coelute from the column ensemble. These methods enabled the complete separation of an 18-component vapor mixture of common solvents in air in 3.5 min.     

Hot Plate Method with Two Simultaneous Temperature Measurements for Thermal Characterization of Building Materials

This paper presents a study of the hot plate method with two simultaneous temperature measurements, on the heated and unheated faces of a sample to characterize. The thermal properties of polyvinyl chloride, plaster and laterite were considered to be a representative range of building materials. A 1D quadrupolar model was developed to represent the temperature evolution on the two faces over time. Three-dimensional numerical modeling of a quarter of the testing device with COMSOL software allowed defining the domain of the 1D hypothesis validity. The analysis of estimation possibilities of materials’ thermal characteristics, with the developed method, revealed that thermal effusivity can be accurately estimated by using the temperature of the heated face at the beginning of heating. We showed that the simultaneous use of two temperatures enables the estimation of the thermal conductivity with a greater accuracy and over a shorter time interval than using the temperature of the heated face alone. We also demonstrated that under certain conditions (samples with a high ratio of thickness to width) the method with two temperature measurements enabled the estimation of the thermal effusivity and conductivity, while the method with one temperature allowed only the thermal effusivity to be estimated, because of 3D effects. This conclusion was confirmed by experimental results obtained with a mortar sample.     

考虑生产过程时间的柔性作业车间调度优化

通过研究生产过程时间,重新细分和定义等待时间,建立包括运输时间、调整时间、故障时间、等待时间、加工时间在内的柔性作业车间生产过程的时间模型,研究了柔性作业车间调度优化问题并设计了混合遗传算法的求解算法。最后,采用经典柔性作业车间调度用例,验证和对比了柔性作业车间调度的结果。结果表明,基于生产过程时间模型研究柔性作业车间调度问题,其优化性能有较好的改进,具有更好的实际应用价值。     

具有模糊时间窗的多模式联运建模及优化

以考虑用户偏好的模糊时间窗多式联运为研究对象,建立了基于图状结构的模糊时间多式联运模型。在分析模型特征的基础上,设计了基于正交试验的混合田口遗传算法实现路径及运输方式的组合优化。通过考虑不同用户偏好的5个任务来考察模型和优化算法的有效性。计算结果表明,该算法能有效求解出满足用户偏好的路径及运输组合方式,为物流企业决策提供依据。     

高长径比TiO2纳米管阵列的调控制备及其光阳极性能

采用较高粘度的有机溶液作为阳极氧化电解质溶剂制备了TiO₂纳米管阵列. 通过探讨阳极氧化工艺参数对纳米管形貌的影响, 研究出高长径比TiO₂纳米管阵列的制备工艺, 同时对TiO₂纳米管作为染料敏化太阳能电池光阳极的光电性能进行了测试, 并讨论了TiO₂纳米管的形貌对电池性能的影响. 结果表明：提高氧化电压和延长时间有利于获得高长径比纳米管, 在含0.5wt%NH₄F乙二醇电解质中50V氧化17h可制备出长径比为313.6的TiO₂纳米管阵列. TiO₂纳米管(在含0.5wt%NH4F乙二醇电解质中40V氧化13h)作为染料敏化太阳能电池光阳极可得到开路电压为0.723V、短路电流为2.15mA/cm²的光电性能.     

Study of Standard Mica Capacitors with Respect to Time and Temperature

Standard mica capacitors manufactured by General Radio are widely used by National Metrology Institutes (NMIs) and other calibration laboratories. The temperature coefficient and stability of standard mica capacitors play significant role in precision measurement. This paper reports the study of standard mica capacitor (General Radio make) with respect to time and temperature. This study is useful for calibration laboratories while reporting measurement results in Proficiency Testing, Inter Laboratory Comparison programmes and calibration reports.     

Column performance and stability for high-speed vacuum-outlet GC of volatile organic compounds using atmospheric pressure air as carrier gas

The development of lightweight, portable GC instrumentation is handicapped by the need for compressed carrier gas to drive the separation. The use of air as carrier gas eliminates the need for compressed gas tanks. If a vacuum pump is used to pull carrier gas and injected samples through the column, atmospheric pressure air can be used as carrier gas. Vacuum outlet operation also improves performance for high-speed separations by reducing detector dead time and by shifting optimal carrier gas velocity to higher values. Under vacuum outlet conditions using atmospheric pressure air as carrier gas, a 6-m-long, 0.25-mm-i.d. capillary column can generate approximately 12,500 theoretical plates, and a 12-m-long column can generate approximately 44,000 plates but with a 3-4-fold increase in separation time. The principal issues in column selection for high-speed GC with air as a carrier gas are efficiency and stability. Several bonded and nonbonded stationary phases were evaluated for use with air as carrier gas in the analysis of volatile organic compounds of interest in airmonitoring applications. These include dimethylpolysiloxane, 50% phenyl-50% methyl polysiloxane, 50% cycanopropylphenyl-50% methyl polysiloxane, trifluoropropyl polysiloxane, poly(ethylene glycol), and dicyanoallyl polysiloxane (nonbonded). The dimethyl polysiloxane and the trifluoropropyl polysiloxane columns showed good efficiency and no significant deterioration after 5 days of continuous operation with air as carrier gas. The 50% phenyl-50% methyl polysiloxane and the 50% cycanopropylphenyl-50% methyl polysiloxane columns showed poorer efficiency, and the poly(ethylene glycol) and dicyanoallyl polysiloxane columns showed excessive deterioration in air.     

Raspberry‐Shaped Thermochromic Energy Storage Nanocapsule with Tunable Sunlight Absorption Based on Color Change for Temperature Regulation

A novel raspberry‐shaped thermochromic energy storage nanocapsule (RTESN) is successfully designed and fabricated with switchable sunlight absorption capacity based on color change for temperature regulation. The RTESN is developed by grafting amino‐modified silica shell thermochromic nanoparticles (amino‐TLD@SiO₂) on the surface of epoxy‐functionalized energy storage nanocapsules (paraffin@PSG), with a total particle size about 450 nm. RTESN exhibits a deep color under low temperatures, which can absorb sunlight for heating. During the continuous thermal energy supply, paraffin@PSG is capable of storing thermal energy owing to its large latent heat capacity of 118.7 J g^–1, thereby maintaining the slow temperature increase. When the temperature is higher than the phase change temperature of paraffin@PSG, the color of amino‐TLD@SiO₂ turns to white with more reflection of sunlight so that it reduces the absorption of thermal energy and prevents the further increase of temperature. The thermal regulation behavior is confirmed by setting up a wooden house with the surface covered with RTESN. Compared with the blank wooden house, the RTESN covered wooden house (RTESN‐H) displays thermal insulation performances during heating and cooling with a maximum temperature difference of 7 °C.