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.     

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.     

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.     

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。     

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.     

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.     

Polymer-Coated Fiber Bragg Grating Sensors for Simultaneous Monitoring of Soluble Analytes and Temperature

A new fiber-optic sensor for simultaneous measurement of water-soluble analytes and temperature with polymer-coated fiber Bragg gratings (FBGs) is proposed. As an application of the approach, simultaneous monitoring of the concentration of sugar or potassium chloride (KCl) and temperature has been achieved. Changes in these environmental parameters result in different extents of either red- or blue-shifts of the Bragg resonance wavelengths of the gratings. It has been found that polyimide-coated FBG responds to variations of both temperature and concentrations of soluble analytes, while acrylate-coated FBG is sensitive to environmental temperature only. The experimental results showed that the temperature sensitivity of the acrylate-coated FBG, temperature, sugar, and KCl concentration sensitivities of the polyimide-coated FBG are 0.0102 $~hbox{nm}/^{circ}hbox{C}$ , 0.0094 $hbox{nm}/^{circ}hbox{C}$, 0.0012 $hbox{nm}/^{circ}hbox{Bx}$ , and 0.0126 nm/M, respectively. The sensing mechanism of the polyimide-coated FBG lies in the hygroscopic properties of the polyimide coating, which result in the change of the strain of the fiber and, thus, the optical properties of the grating. Since the sensor detects the analytes that swell the polyimide coating and different analytes induce different swelling effects, the sensor can detect different analytes without prior knowledge once a calibration curve is developed.      

具有时间窗的开放式车辆路径的改进微粒群算法

分析了车场开放的带时间窗的车辆路径问题,在完成配送服务的车辆数目不确定的条件下,建立了该问题的数学模型,同时运用改进的微粒群算法求解该问题,算法采用一种基于客户的序数编码方法构造初始种群,对微粒群算法的进化方程进行了改进,使改进微粒群算法的搜索过程具有自适应性。最后根据第三方物流配送的实际,基于问题的不同目标,运用数值检验了模型和算法的有效性。     

允许缺货的可控提前期供应链库存优化与协调

将单个企业的可控提前期库存模型拓展到供应链环境中,并考虑了允许部分缺货后补的情形,分别建立了分散决策和联合决策情形下允许部分缺货后补的可控提前期供应链库存优化模型,并提出价格折扣机制来协调供应链成员的利益.采用数值实验方法,对所建的库存优化模型和协调机制进行了分析,结果表明:随着缺货后补比例的不断减少,供应链必须不断增大订货批量和压缩提前期以提高顾客服务水平;价格折扣机制可以使得允许缺货的可控提前期供应链达到协调的目的.     

分布式光纤光栅应变和温度同时测量系统

设计了分布式光纤光栅应变和温度同时测量系统,光源为时钟脉冲宽带光源,结合时分和波分复用技术解决光纤光栅传感网络的复用寻址问题,选用不同包层直径光纤相熔接的应变补偿法传感头设计方案,实现了温度和应变的同时测量.采用阵列波导光栅技术对传感信号进行解调,通过理论分析证实了系统方案的可行性.系统对应变和温度的测量范围为0～2500 με和25～120℃,误差分别为±17 με和±1℃.     

Determination of Pentachlorophenol and Its Oil Solvent in Wood Pole Samples by SFE and GC with Postcolumn Flow Splitting for Simultaneous Detection of the Species

An alternative approach is described for the measurement of pentachlorophenol (PCP) and its oil solvent in wood samples by supercritical fluid extraction (SFE) and gas chromatography (GC). The determination is achieved over a single chromatographic run using postcolumn flow splitting for simultaneous ECD/FID detection of the SFE extracted species. First, PCP and oil components are quantitatively extracted from a 0.3-g wood sample using 10% MeOH/CO(2) supercritical fluid at 0.65 g/mL and 120 °C. An aliquot of the SFE solution is then mixed with 10 mL of a buffered aqueous phase at pH 9.4. After PCP is acetylated by the addition of 500 μL of acetic anhydride, it is followed by its extraction with 2.00 mL of hexane along with oil. Then, 0.5 μL of supernatant organic phase is injected into the GC for a selective and simultaneous determination of the species. The method has a linear response over 3 orders of magnitude for both species with a linear regression correlation coefficient higher than 0.98 (95% confidence limit) and an absolute detection limit of 60 ng of PCP and 80 μg of oil per 0.1-g wood sample. The precision (relative standard deviation) is 4% for PCP and 1% for oil as established for a typical average concentration sample. The accuracy of the SFE GC-ECD/FID combined technique for PCP and oil was assessed by analyzing wood samples collected from newly and in-service PCP/oil-impregnated red pine poles.     

High-precision Tunable Retardation Plate for Use with Visible and Ultra-violet Polarized Light

A variable retardation plate suitable for polarizing optics in the visible and ultra-violet has been developed. It is based on the photoelastic effect induced by lateral compression of a rectangular plate of fused silica. A special pressure frame employing hydraulic pressure gives very even compression, and the stress pattern induced is uniform to within 1 per cent over most of the plate area. A pneumatic ballast system has also been developed to stabilize the pressure, which maintains the retardation constant to within ½ per cent over a period of hours. Possible applications of the retardation plate in optical instrumentation and in the accurate measurement of pressure are discussed.     

Axial and Extra-axial Responses in Aberrated Optical Systems with Apodizers. Optimization of the Strehl Ratio

Abstract

The effect of non-uniform transmission filters on the axial and extra-axial responses of aberrated optical systems is studied. The axial Strehl ratio (SR) is increased by varying the filter transmission function and the extra-axial SR by shifting the filter position along the axis of the optical system. It is shown that a filter which optimizes the axial SR can also improve the extra-axial SR. There are some positions of the filter for which the total results are improved. These positions are explained from the lack of radial symmetry of the wave aberration. The filters which improve the SR are also studied in terms of energy transmission.     

涡旋真空泵运行工况温度场的ANSYS模拟与研究

在涡旋真空泵相关试验的基础上,通过大型有限元分析软件ANSYS对其工作过程的温度场进行了模拟分析.相关结果表明,软件分析基本上可以反映涡旋真空泵运行过程中温度场分布及变化情况,从而为其设计参数及相关因素的确定提供有效的分析手段.     

Simultaneous monitoring of volatile selenium and sulfur species from se accumulating plants (wild type and genetically modified) by GC/MS and GC/ICPMS using solid-phase microextraction for sample introduction

A sensitive method for determining ultratrace volatile Se species produced from Brassica juncea seedlings is described. The use of a new commercially available GC/ ICPMS interface in conjunction with solid-phase micro-extraction is a promising way to perform these studies. The addition of optional gases (O2 and N2) to the argon discharge proved to increase the sensitivity for Se and S as well as for Xe, which as a trace contaminant gas, was used for ICPMS optimization studies. However, the optimization parameters differ when an optional gas is added. In the best conditions, limits of detection ranging from 1 to 10 ppt can be obtained depending on the Se compound and 30 to 300 ppt for the volatile S species. The use of GC/MS with similar sample introduction permits the characterization of several unknown species produced as artifacts from the standards. The method allows the virtually simultaneous monitoring of S and Se species from the headspace of several plants (e.g., onions, garlic, etc.) although the present work is focused on the B. juncea seedlings grown in closed vials and treated with Se. Dimethyl selenide and dimethyl diselenide were detected as the primary volatile Se components in the headspace. Sulfur species also were present as allyl (2-propenyl) isothiocyanate and 3-butenyl isothiocyanate as characterized by GC/MS.     

钢水连续测温传感器的准确度提高和结构优化

为提高钢水连续测温传感器的准确度和灵敏度,以传感器所形成的在线黑体空腔的实际结构模型、带盖半球-圆筒形腔体为研究对象,建立了结构参数为二次关系的积分发射率的计算公式,并推导出全照区、半照区和不可见区域的自动划分计算公式.详细分析了传感器结构,即黑体空腔的长度、半径、孔径、腔口与探测器之间的距离,以及探测器接收面半径对积分发射率的影响,并在此基础上给出了传感器的优化参数.