High temperature silylation of glass capillary columns

This paper describes the results of a study on the deactivation of the surface of glass capillary columns by high temperature silylation (HTS). The different steps, leaching, washing, dehydration and HTS were optimized. A practical procedure yielding a high percentage of very good columns is given. The influence of leaching and HTS on the temperature stability and coating efficiency of capillary columns coated with OV-1 was studied. The inertness of the glass surface after HTS is demonstrated by several examples.     

Preparation of apolar glass capillary columns by the barium carbonate procedure

As an extension of previous reports, the barium carbonate procedure has been optimized in detail for the preparation of apolar columns. The aim was to produce optimum overall column characteristics, and to maintain them unchanged under the prolonged influence of the highest possible temperature. The main parameters under optimization were glass variety, leaching of glass surface with aqueous HCl, and amount of barium carbonate deposited, while deactivation and coating were kept constant. The basic column characteristics were adsorption properties and thermostability of deactivation, acid/base behaviour and separation efficiency. They were determined by a new, quantitative testing procedure. Intense leaching was able to eliminate almost totally the differences between glass varieties and to create a well-defined glass surface. While untreated glass, leached glass, and barium carbonate treated glass showed specific weak points in the respective column quality, the combination of leaching and barium carbonate treatment yielded the highest and most stable quality. Some technical modifications of the preparation procedure are described, including deactivation in the gas phase, and use of pentane as a solvent for static coating.     

Glass capillary gas chromatography of highly polar solutes like diols,acids and amines deactivation of fused silica and pretreated alkali glass support surfaces

Summary The method of support surface deactivation by PSD (alkylpolysiloxane degradation) at temperature between 300 and 450°C previously described was used to deactivate both fused silica and alkali glass surfaces of capillary columns. The latter surfaces had to be pretreated before deactivation with aqueous HCl leaching or by the dealkalisation method using flowing HCl gas at 450°C and subsequent rinsing with water for alkali removal. Excellent alkylpolysiloxane columns with regard to tailing and irreversible adsorption of highly polar solutes have been obtained on both fused silica and the pretreated alkali glass. Fused silica does not require pretreatment before deactivation by the PSD-method, however. Good polyethyleneglycol (Carbowax 20 M) columns can also be obtained by coating the two types of surfaces when no deactivation is necessary. Deactivation by the PSD method cannot be applied in this case because polar stationary liquids do not adhere to alkylpolysiloxane deactivated surfaces. Sample capacity problems arising when separating highly polar solutes with non-polar stationary phases have also been investigated.     

硫酸钡微晶改性毛细管柱的制备及其分离性能的研究（Ⅱ）

本文在中等极性和强极性玻璃毛细管柱研究的基础上（１），对弱极性和非极性固定液在硫酸钡微晶改性表面上的涂渍情况作了详细的研究。研究表明，只要对这种改性表面进行钝化处理，即可途渍出高效弱极性和非线性毛细管柱。     

Wide-bore glass capillary columns for gas chromatography. Their preparation and application

Summary Methods for the preparation of wide-bore glass capillary columns for gas chromatography are presented. The pretreatment of the columns (etching, carbonization, deactivation and/or surface-coating with porous materials), and the coating of them with polar or apolar phases (preferably by the static method) is described. The performance of the columns prepared is evaluated and a number of applications are given, such as analysis of volatile compounds, pesticides, lipids and GC/MS analysis. In some respects, the wide-bore glass capillaries have advantages over the narrow-bore types. They can be installed very easily in GC-instruments, and permit the analysis of larger samples. A system of collecting separated sub-g fractions in glass capillary traps, which makes direc re-injection from these traps possible, completes the methods presented.     

Flexible soft glass capillary columns vs. flexible fused silica capillary columns for gas chromatography-a critique

The gas chromatographic use of flexible thin walled soft glass capillary columns coated with non-polar stationary phases is compared to similar columns made of fused silica glass. With non-polar soft glass columns, the use of surface roughening viagaseous HCI followed by a Carbowax 20 M pretreatment gave adsorptive phenomena, and thermal instability. With very polar soft glass columns where a variety of cyanopropyl silicone phases were coated directly onto the NaCI crystal matrix, adsorptive effects were again prominent and frequent break-down in film stability with time, was also observed. These undesirable effects were due to the presence of metal oxides in the soft glass. Attempts to remove these materials from the thin walled soft glass surface by means of acid leaching produced significant brittleness. This deleterious result was further increased by attempts at high temperature silylation or polysiloxane deactivation. In sharp contrast, the fused silica surface was essentially free of metal oxides and the surface silanol groups are easily neutralized by silylation or polysiloxane deactivation techniques. No brittleness was observed following these procedures. An increasing series of high molecular weight, viscous, polymeric vinyl containing non-polar and highly polar stationary phases have been produced which readily wet the surface of the fused silica and are easily crosslinked in the presence of free radical generators. These columns are essentially free of all the problems noted with flexible thin walled soft glass. When all of the parameters involved in the fabrication of a glass capillary column are assessed, it appears at this time, that the flexible fused silica glass column with cross linked phases approaches the “ideal” capillary column.     

Increased thermostability of non-polar wall-coated open tubular columns

A method of deactivating the inner surface of glass capillary columns is described, which can be used at 350°C without detoriation. A non-polar liquid phase was prepared from a commercially available liquid phase which, when coated on a glass surface, can withstand temperatures of 325°C for isothermal analysis and 350°C for temperature-programmed analysis. After deactivation, the column was coated using the static coating method. Then it was conditioned, tested and kept for 48 hours at 35O°C before being used for the analysis of a mixture of chlorinated pesticides.     

Effect of film thickness and supercooling on the performance of cholesteryl cinnamate liquid crystal capillary columns

Improved separations of the isomers of olefinic aliphatic insect pheromones were obtained on cholesteryl cinnamate glass capillary columns by operating in the supercooled temperature range of the liquid crystal. Capillary columns were prepared with varying film thickness of the stationary phase; choice of the correct film thickness ensured optimum retention for a wide range of compounds within the most effective temperature range of the liquid crystal. The deactivation procedures described made the liquid crystal columns suitable for separation of the geometric isomers of polar and nonpolar compounds.     

Preparation of thermally stable phenylpolysiloxane fused silica capillary columns. Optimization and evaluation of the deactivation by capillary GC and solid state 29Si NMR

The deactivation of fused silica capillary columns with a laboratory-made poly-diphenylvinylmethylhydrosiloxane copolymer has been investigated. The deactivation obtained at different temperatures and reaction times is characterized with a dual column capillary GC system [1]. In parallel, the effect of the silylation temperatures and reaction times on the nature, the structure, and the chemical properties of the deactivation layer has also been studied by solid-state ²⁹Si NMR spoctroscopy. A fumed silica, Cab-O-Sil M5, was used as a model substrate for these spectroscopic studies. The deactivated fused silica capillaries show an excellent thermal stability (up to 400°C), a high resistance to solvolysis, and a minimal interaction to various critical test components. A good wettability of the fused silica capillary columns deactivated with this reagent was confirmed by successful subsequent coating with polysiloxanes with different phenyl contents.     

Alkylpolysiloxane glass capillary columns combining high temperature stability of the stationary liquid and deactivation of the surface

Summary A new method of making alkylpolysiloxane (OV 1, OV 101, OV 17, Dexsil 400, SE 52, SE 54) columns with high stability at temperatures above 300°C of both the stationary liquid itself (low bleeding) and of the surface deactivation (no tailing of polar solutes with extended use at temperatures beyond 250°C) is described. The best results were achieved on dealkalinized alkali glass but also on borosilicate surfaces which have been additionally HF treated before coating in both cases. The procedure can also be applied to leached alkali and borosilicate surfaces successfully. The best deactivations of the glass surface are attained in a two step procedure: firstly by treatment with gaseous HF/N₂ mixture and secondly by simple heating of the coated and closed column at temperatures between 350° and 450°C for several hours. The tailing behaviour of such columns for polar solutes is considerably improved by this procedure as shown by test chromatograms. The procedure can also be applied to leached alkali and borosilicate surfaces successfully.Extract also presented at the 8th National Meeting on Analytical Chemistry of the Swedish Chemical Society, Lund, June 1979 and at the 10th International Symposium on Chromatography and Electrophoresis, Venice, Italy, June 1979.     

Preparation,evaluation, and comparison of wide bore (320 μm) and narrow bore (50 μm) cyanosilicone-coated capillary columns for gas chromatography

The preparation of wide bore (320 μm) and narrow bore (50 μm) fused silica capillary columns is described for immobilized cyanopropyl substituted silicones containing 60 and 88% substitution. The effect of high temperature deactivation with cyanopropylcyclosiloxanes was studied with a special test mixture. Curing was achieved with dicumyl peroxide or azo-tert-butane. The columns were evaluated and compared in terms of efficiency, activity, polarity, and temperature stability. Different coating methods were compared for the narrow bore columns. The activity of the 60% cyanopropyl columns that had been immobilized with dicumyl peroxide was significantly larger than for azo-tert-butane immobilized columns. The polarity of polar columns appeared to depend greatly on column temperature and is completely different for wide and narrow bore columns.     

Comparison of dynamically coated SE-54, SP-2250 and carbowax 20M wall-coated open tubular (WCOT) glass capillary columns,prepared after surface pretreatment with Superox™-4 or with BaCO3

A new surface pretreatment for the preparation of wall-coated open tubular (WCOT) glass capillary columns has been evaluated. This technique involves the application of a non-extractable layer of Superox?-4, a 4,000,000 MW polyethylene glycol, to the glass surface as a pretreatment and deactivation agent. Unlike other polyethylene glycols, Superox-4 is stable at high temperatures (> 300°C) in the absence of oxygen, coats smoothly onto a bare glass surface and resists droplet formation. WCOT columns (SE-54, Carbowax 20M, and SP-2250) prepared using this technique are compared to columns prepared using a modified Grob [2,3] BaCO₃ procedure. The Superox-4 pretreated columns were equal or superior in quality to the BaCO₃ pretreated columns, based on the appearance of an activity standard and the effective theoretical plates (N_eff) per meter. Chromatograms showing practical application of the WCOT columns prepared using both methods is given.     

Free release static coating of glass capillary columns; rapid coating at lower temperatures and elevated pressures

The coating speed upon static coating of glass capillary columans was evaluated in terms of inner diameter and length of the column, viscosity and pressure of solvent vapor, etc. From the equation obtained it can be shown that a smaller diameter of a microbore column restricts solvent vapor transfer to the orifice of the column drastically. To compensate for this restriction, a higher pressure at the meniscus is needed. As an alternative to using a higher coating temperature, application of more volatile solvents such as n-butane and isobutane is proposed. Several glass capillary columns (130 μm i.d.) were coated with SE-54 dissolved inpentane-acetone mixed with n-butane or isobutane and the column performances were evaluated. Selection of these solvents permitted free release static coating of ca. 100 μm columns at lower or even ambient temperatures and they were equally suitable as commonly applied solvents (e.g. pentane) to coat highly efficient columns.     

The preparation of thick-film glass capillary columns

A detailed method for the routine preparation of glass capillary columns is presented. The method consists of coating a glass tube with quartz powder prior to pulling the tube into a capillary. The inner surface of the capillary consists of an even distribution of quartz particles fused to the walls. This surface has been found readily deactivated by standard procedures and ideal for the preparation of thick-film glass capillary columns. The method has been thoroughly tested in two independent laboratories to ensure that the procedures described are reproducible.     

A problem in etching Pyrex glass capillary columns

Recent attempts to reproduce a literature method for etching of Pyrex glass capillary columns with ?etching ether”? resulted in reduction of the columns to dust through a violent explosion. Although modifications of the method produced etched columns, we found that less than satisfactory results were achieved. Introduction of etching ether by simply coating the column with a thin film of the ether produced an evenly etched column with well defined whiskers. Several observations made during the etching process will also be discussed.     

Determination of adsorption by fluorescence in gas chromatography

PMBF₂, a pyrromethene pigment, can be used in gas chromatography. Because of its fluorescence, adsorption sites on glass columns and connections can be traced in situ. The compound can be employed to check the inertness of glass surfaces after deactivation procedures. Some applications are described.     

Free release static coating of glass capillary columns; Static coating at elevated pressure — Theoretical considerations and practice

Summary Static coating of glass capillary columns has hitherto solely been carried out by evaporation of the stationary phase solvents under vacuum conditions. However, since a solvent vapour pressure higher than the external pressure is the only requirement for the vapour to flow out of the column, evacuation should not be necessary. Several important factors in the static coating procedure, such as mass (solvent vapour) — and heat transfer, heat of vaporisation of the solvent and viscosity of the stationary phase solution at elevated temperature and outlet pressure are discussed, principally to rationalise an improved static coating procedure. The alternative, so-called free-release static coating procedure, was evaluated practically by coating several columns with OV-101 and SE-30. Coating speed was found to be rapid and relatively constant whereas coating efficiency was between 80 and 100%.     

Comparison of surface modification techniques used for the preparation of wall coated open tubular glass capillary columns

Summary Comparison of different techniques for modifying internal glass surfaces to accept a substrate loading on wall coated open tubular columns (WCOT) were examined. Inner surfaces pretreated with a non-extractable Carbowax 20M layer, barium carbonate and silica whiskers were prepared and coated with a Carbowax 20M liquid phase. The columns were evaluated for efficiency, acidic-basic and adsorption properties, thermal stability and coating efficiency. Column performances were also assessed for deactivated surfaces. Each column was applied to a standard mixture of Aroclor 1016.     

The nature of the structural gradient in epoxy curing at a glass fiber/epoxy matrix interface using FTIR imaging

The curing process of an epoxide system was studied at the interface formed between a silane-coated glass fiber and an epoxy matrix. The gradient in the structure of the epoxy resin as a result of the cure process at the fiber/matrix interfacial region was monitored by FTIR imaging. For comparison, the epoxy curing at the interface formed between the epoxy resin and (a) an uncoated glass fiber and (b) a polyorganosiloxane (obtained from the silane used for the glass-fiber coating) were also monitored. Chemically specific images of the OH and the H-N-H groups near the interface region were obtained. These images suggest that there is a chemical gradient in the structure of the matrix from the fiber surface to the polymer bulk due to different conversions. The basis of the different kinetics of the curing reactions is a result of amino group inactivation at the interface. This deactivation translates into an off-stoichiometry of the reaction mixture, which is a function of the distance from the surface of the glass fiber.     

Glass capillary columns with liquid crystalline stationary phases for gas chromatography. The influence of the pretreatment of the inside tube wall

Summary The importance of capillary columns prepared with a liquid crystalline stationary phase are increasing. It is known that the interaction of the liquid crystals molecules with the glass capillary wall may strongly influence selectivity and efficiency of the column. The paper reports on systematic investigations on the correlations between the pretreatment of the inside glass capillary surface, the chemical nature of the liquid crystal and the chromatographic properties of the columns obtained. Two types of matrix were investigated: barium carbonate and barium carbonate with subsequent deactivation with Carbowaxes. Three liquid crystals with different relative polarity (terminal group polarity) and nematic mezophase transitions were used. Deposition of barium carbonate, if necessary, with a secondary Carbowax treatment was found as an excellent capillary wall pretreatment method. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984