非平衡塔板理论的几个问题

本文用非平衡方法对塔板理论进行了重新处理,导出了描述塔板过程的统一方程（平衡或非平衡）如下：（注：符号ｐｆ（ｒ,ｎ）表示交换ｎ次后第ｒ号塔板流动相中的物质分数;符号ｑｆ（ｒ,ｎ）表示交换ｎ次后第ｒ号塔板固定相中的物质分数）经计算机数值计算,得到如下初步结果：（１）色谱峰是不对称峰,其形状与流速有关。流速增大,不对称性将增大。流速的改变,也会引起峰形的其它改变。（２）色谱峰的峰宽与流速有关。流速增大,峰宽（以塔板数为量纲）将增大。（３）色谱峰的峰高与流速有关。流速增大,峰高将减小。     

PET/SiO_2纳米复合材料的内耗研究

利用内耗和DSC的方法研究了不同纳米粒子含量PET/SiO2纳米复合材料和纯PET弛豫性能的变化,并计算出次级弛豫峰的激活能和峰高以及主级弛豫的激活参数和峰高.结果发现内耗峰的峰高和主弛豫的激活参数以及次级弛豫的激活能随纳米SiO2的增加而减小.一方面内耗峰的峰高主要是PET的非晶区的分子链或基团运动产生,因此纳米粒子的高效成核效应,促进PET结晶成核,非晶区减小,导致内耗峰减小.另一方面由于纳米粒子与PET产生化学接枝以及氢键等作用,对链段的运动起到了一定的限制作用,导致主弛豫的激活参数和次级弛豫的激活能的增加.因此纳米SiO2颗粒与PET基体之间的化学和物理相互作用导致了PET链段的弛豫特性的变化.     

高效液相色谱峰压缩中灵敏度增加值与峰压缩因子的关系研究

以从塔板理论得到的色谱流出曲线为基础,推导了高效液相色谱(HPLC)双流动相分离场中实现峰压缩时,峰压缩因子(峰压缩后的半峰宽与未进行峰压缩时的半峰宽的比值)和峰高表示的灵敏度变化(峰压缩后的峰高与未进行峰压缩时的峰高的比值)的关系,结果表明峰高表示的灵敏度增加值等于峰压缩因子的倒数.并用色氨酸、香豆素、苯和2-硝基酚在不同速率差实现堆积时的相关参数进行了验证.实验结果表明,这些化合物在各个峰压缩条件下的峰压缩因子倒数和实际灵敏度增加值相等,实验结果与理论推导结果一致.考察了该关系式在实际样品测定中的应用,结果表明灵敏度增加值等于峰压缩因子的倒数,这也与理论部分的结果一致.     

CVD法制备碳纳米管的TG-DTA研究--温度对CVD法制备碳纳米管的影响

基于碳纳米管粗产品中无定形碳和不同直径碳纳米管对氧的反应活性的差异,通过差热-热重(TG-DTA)方法,结合透射电镜(TEM)和X射线衍射(XRD)的测试结果,研究了合成温度对以乙炔气体为碳源,用CVD法制备碳纳米管的石墨化程度、碳纳米管直径以及直径分布的影响.结果表明:反应中,由于催化剂Co/SiO2中活性组分(Co)微晶随合成温度的升高而增大,导致所制备的碳纳米管的直径增大,从20～30 nm(650℃)增加到30～50nm(750℃).碳纳米管的石墨化程度随着反应温度的升高而增加.XRD实验结果还表明,当合成温度从650℃增加到850℃时,2θ值从25.8°增加到26.8°,(002)晶面的层间距从3.45 A减小到3.32 A,即随着合成温度的升高,碳纳米管(002)晶面的层间距减小.通过DTA放热峰的峰温和半峰宽的分析得出,无定形碳的放热峰峰温Tp＜380℃,其含量随着温度的升高而减小.碳纳米管的DTA放热峰的峰温Tp随着碳纳米管的直径和石墨化的程度的增加而升高,半峰宽随着碳纳米管的直径的分布范围增大而增宽.低温(650℃)有利于生成直径小且均匀的多层碳纳米管(20～30nm),而高温(大于750℃)则有利于生成直径大的多层碳纳米管(大于30～50 nm).     

La2O3对Yb3+掺杂的氧化钇透明激光陶瓷性能的影响

本文研究了La2O3的含量对(Yb0.05 Y0.95)2O3透明激光陶瓷的结构性能和烧结性能的影响.结果表明:随着La2O3含量的增加,拉曼光谱特征峰发生红移,声子能量降低,半高宽增大,相对强度先增大后减小;同时密度、相对密度和透过率都增大,陶瓷的晶粒减小,而当La2O3含量继续增加时,晶粒基本保持不变.但适量的La2O3掺杂量对(Yb0.05Y0.95)2O3透明激光陶瓷的发射性能影响不大.最合适的La2O3添加量为10at%,最合适的烧结温度为1700℃,最后样品的直线透过率可达到75%.     

热历史对尼龙1212熔融行为的影响

利用DSC方法研究了不同热历史条件对尼龙1212熔融行为的影响.不同的热历史条件下,在DSC曲线上,观察到尼龙1212产生2个或3个熔融峰,依据聚合物结晶理论,对各峰的来源进行了分析.在160℃下不同温度退火120 min的尼龙1212样品DSC曲线上,低温结晶熔融峰主要由低温结晶形成的一些微晶体或者片晶熔融产生,其晶体完善程度较差,熔融峰值较低,峰面积较小;主熔融峰是由样品在淬火过程中形成的晶体和升温过程中低温结晶形成的晶体的熔融重结晶形成较为完善的晶体熔融所产生,熔融峰值较高,峰面积较大.在不同的升温速率条件下,熔融峰温度有所移动,表明不同升温速率条件下产生的熔融峰的结晶晶型是相同的.在不同结晶时间下结晶,延长结晶时间对较高完善程度晶体的生长有利.在不同温度下依次退火处理的样品,熔融产生两个附加峰,这两个附加峰的峰温都比它们相应的退火温度高,而峰高和峰面积随退火温度降低而减小.根据等温结晶结果,由Hoffman方法确定了尼龙1212的平衡熔融温度为202.8℃.     

高效液相色谱中苯甲醛的在线堆积研究及其应用

以乙腈和水为流动相,研究了苯甲醛在苯基柱和C18柱双柱串联体系中的在线堆积行为.结果表明,苯甲醛在苯基柱-C18柱组合体系中能实现有效堆积,且速度差越大堆积得越好.在实验最佳堆积条件下,堆积因子为4.6,峰高增加5.4倍,该堆积条件下保留时间,峰面积,峰高和半峰宽的RSD值分别为1.2%, 4.2%,3.4%和0.80%.将苯甲醛的在线堆积效应用于单胺氧化酶(MAO)酶活性测定样品,信噪比提高了6.9倍,检测灵敏度显著提高.实际样品测定中保留时间,峰面积,峰高,半峰宽,塔板数和信噪比的RSD值分别为0.1%, 4.6%,5.0%,0.7%,1.2%和4.67%,精密度满足分析测定的要求.     

毛细管胶束电动色谱定量方法研究

在前文中,我们报道了毛细管胶束电动色谱(MECC)的原理、装置,电中性物质的分离以及各物理因素对分离的影响。本文在前文的基础上,对MECC中保留时间重现性,峰高、峰面积定量的重现性、线性和检测限等进行了较为系统的研究,并讨论了进样时间对峰高和峰面积的影响。     

聚丙烯DSC测试影响因素探究

以聚丙烯注塑成型样品为例,分别以不同温度对样品进行状态调节、不同升温速率消除样品热历史和不同降温速率冷却对样品进行DSC实验,分析其对测试结果的影响.结果表明:以不同温度对样品进行状态调节后进行实验,其第一次升温熔融峰温受状态调节温度影响出现先增大后减小,最大偏差2℃,对随后的降温过程和第二次升温过程无影响;以5℃/m...     

NaOH溶液中碱浓度、氧气压力以及温度对Pt电极上氧气还原反应的影响

设计制作一种新型耐压电化学池并采用循环伏安(CV)和线性扫描伏安(LSV)技术系统研究了碱浓度、氧气压力以及温度对NaOH溶液中氧气还原反应(ORR)的影响.研究结果表明,碱浓度、氧气压力和温度对ORR动力学和热力学都有很大的影响.随着碱浓度增大,ORR过程逐渐由2电子(生成HO2-)转为1电子(生成O2-)反应,并且由于氧气溶解度减小和体系粘度增大ORR过程受到很大抑制.增大压力可以明显增加氧气溶解度,从而从动力学上促进ORR过程;同时计算得到了氧气在不同浓度NaOH溶液中的亨利系数.随着介质温度升高,由于氧气反应活性增强、扩散系数增大和溶解度减小的共同作用,表现出在给定浓度下存在一最佳温度使得ORR峰电流达到最大.     

Investigation of the boron nitride/polybenzoxazine interphase

The influence of a hexagonal boron nitride powder surface on the polymerization of a benzoxazine monomer is examined by differential scanning calorimetry (DSC). By varying the thickness of the benzoxazine coatings on boron nitride particles, a distinct influence of the surface substrate on the polymerization reaction could be observed. At a coating thickness calculated to be on the order of a monolayer, the heat of reaction is reduced, while the exothermic peak temperature and peak width at half height are increased relative to that of the neat resin values. The reduced heat of reaction and increased exothermic peak temperature indicate that the boron nitride surface is inhibiting the benzoxazine polymerization reaction. In the intermediate coating thickness region, the heat of reaction increases and the exothermic peak temperature and peak width at half height decrease with increasing coating thickness. With even thicker coatings, the heat of reaction and exothermic peak temperature and peak width at half height reach values corresponding to that of the neat resin and no longer change with thickness. In addition, the influence of surface treated boron nitride particles on the thermal polymerization behavior, as well as the effect of the surface treatment on the viscosity, dynamic mechanical properties, and flexural properties of the filled composites are also investigated. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2360–2372, 1999     

The prediction of the peak width at half height in HPLC

The prediction of the peak width at half height is an important aspect in the optimization of the chromatographic operating conditions. In this paper, a linear relationship, between the peak widths at half height and the retention values with various isocratic elution is observed. In gradient elution, however, the relationship between the peak widths at half height and the so-called invented retention values that correspond to the mobile phase composition by eluting the solute from the column end is developed. We believe that there is almost the same band width at half height inside the column (in unit of length) for different solutes. The peak width at half height in the chromatogram (in unit of time) is mainly determined by the capacity factor of the solute when it is eluted from the column end. The larger the capacity factor of a solute eluted from the column end, the more slowly will be the solute eluted from the column end and the wider will be the peak width at half height. It is possible to predict the peak width at half height in various isocratic and gradient elutions by using this linear relationship.     

Prediction of retention times and efficiency in linear gradient programmed pressure analysis on capillary columns

A method for the prediction of the retention time and the resolution of chromatographic peaks in different experimental conditions by starting from few experimental data measured in isothermal and isobaric analyses was published previously. In this paper, the same mathematical model was implemented for calculating the retention times and the column efficiency in programmed pressure runs. Some models originated from the Golay equation and reported in the literature are compared, and a new modified equation for the calculation of the peak width at half height is proposed. The procedure for the prediction of the retention time and the peak width at half height at programmed pressure of the carrier gas and different column temperature and linear gradient by using retention data of different compounds obtained in few isobaric runs is described. The prediction of the retention time and the separation efficiency of compounds with different polarity gave good results for the programmed pressure runs with linear gradient. The effect of the variation of the initial parameters of the experimental analyses and of the mathematical model on the accuracy of the prediction has been evaluated.     

Prediction of the resolution of capillary columns in different conditions of inlet pressure and temperature

A procedure previously described for the prediction of the plate height of capillary columns operated at different inlet pressure of the carrier gas and at various column temperatures by using few retention data measured under isobaric conditions was modified and improved in order to permit the prediction of the retention times and of the peak widths at various heights. It is therefore possible to calculate the ratio, delta, between the peak width at different heights and the peak width at half height, whose value is used to predict the resolution at different height of two closely eluting peaks. It was found that the delta values do not depend on temperature and inlet pressure and are a characteristic of the used column; they can therefore be used in order to calculate the resolution in any temperature and inlet pressure condition. The method was used to predict the retention time, the peak width and the resolution of polar and non-polar compounds (alkanes, alkenes, chloroalkanes, alcohols, ketones) on capillary columns of different length and polarity by using as the starting data retention and width values measured in three isobaric runs only.     

Peak Profile Analysis in High Field Asymmetric Wave Ion Mobility Spectrometry

High field asymmetric wave ion mobility spectrometry (FAIMS) is a powerful tool to detect and characterize gas-phase ions, while the unsolvable partial differential equation of ions moving in ion drift tube poses a big challenge to FAIMS spectral peak analysis. In this work, a universal and effective model of FAIMS spectral peak profile has been proposed by introducing ion trajectory and loss height. With this model, the influence of the structure of ion drift tube, dispersion voltages, compensation voltages, and carrier gas flow rate on the FAIMS spectral peak characteristics like peak shape, full width at half maximum and peak height is analyzed and discussed. The results show that the influence of different factors on the FAIMS spectral peak profile can be qualitatively described by the model which agrees with the experimental data.     

Temperature effect on peak width and column efficiency in subcritical water chromatography

Subcritical water has been recently employed as the mobile phase to eliminate the use of organic solvents in reversed-phase liquid chromatography. Although the influence of temperature on retention in subcritical water chromatography has been reported, the temperature effect on peak width and column efficiency has not yet been quantitatively studied. In this work, several polar and chlorinated compounds are separated using pure subcritical water on Zorbax RX-C8, PRP-1 (polystyrene-divinylbenzene), Hypersil ODS, and ZirChrom-polybutadiene columns. Isothermal separations are performed at temperatures ranging from 60 degrees C to 160 degrees C. The retention time and peak width of analytes are reduced with increasing temperature. However, the column efficiency is either improved or almost unchanged with the increasing temperature in the low-temperature range (lower than the 100 degrees C to 120 degrees C range), but it is decreased when temperature is further raised in the high-temperature range (higher than the 100 degrees C to 120 degrees C range). Therefore, a maximum in column efficiency is obtained at temperatures within the 100 degrees C to 120 degrees C range in most cases.     

A calculation method for the prediction of effective plate height in capillary gas chromatography

The effective plate height, h_eff, is considered to be a better measure of the efficiency of capillary column than the conventional plate height, h, in isothermal conditions. By using experimental data of 1-alcohols and n-alkanes, 2-ketones and 1-alkenes measured on capillary columns coated with non-polar stationary phases in isothermal and isobaric conditions, the peak width at half height is predicted with a function similar at that of adjusted retention time. The results obtained under different analytical conditions as the head pressure and the temperature of the column confirm the validity of the model, whose parameters are linear, and as a consequence a unique solution is obtained.     

Optimisation of high-performance liquid chromatography with diode array detection using an automatic peak tracking procedure based on augmented iterative target transformation factor analysis

An automated method for the optimisation of high-performance liquid chromatography is developed. First of all, the sample of interest is analysed with various eluent compositions. All obtained data are combined into one augmented data matrix. Subsequently, augmented iterative target transformation factor analysis performs the integrated tasks of curve resolution and peak tracking. Since this type of curve resolution processes all data at once, it can deal with strong peak overlap and reveal the correspondence of compounds between runs, i.e. peak tracking. The retention time and peak width at half height for each component of the sample are determined for every eluent composition. Next, models are built for the retention time and the peak width at half height. These models are used to predict the resolution and the analysis time for each point in factor space. Finally, a multi-criterion decision-making method, Pareto optimality, is used to find the optimum. The method completes all calculations within a few minutes and without user intervention. By means of this procedure, a mixture of three benzodiazepines is successfully separated using a ternary mobile phase. There are two requirements for the automated optimisation method to work correctly. Firstly, all components of the sample must have sufficiently different spectra. Secondly, each compound should have the same spectrum under all experimental conditions.     

On-line testing of gas chromatographic columns with a programmable computing integrator

Summary A program is described which calculates the number of effective plates and the coating efficiency over the entire range of a test chromatogram. The peak widths at half height are derived by assuming a Gaussian peak shape. The interpolated peak width at k=4 is used for computing a standardized number of effective plates. Plate height, column permeability, overall performance and a novel parameter called sampling efficiency are calculated from 5 other figures — i. e. carrier gas code, pressure drop, column length, column temperature and particle size.Dedicated to Dr. Leslie S. Ettre for his 60th birthday.