JPS61183142A - Glass capillary manufacturing method - Google Patents

Abstract

PURPOSE:To obtain a capillary for chromatography contg. a stationary phase with sufficient adhesive power and having a long life and high resolution by sintering a round rod-shaped preform of glass soot formed by a VAD method in the presence of a specified gas and by boring the resulting base material. CONSTITUTION:A round rod-shaped porous preform of SiO2 glass soot is formed on the tip of a starting rod by a VAD method, and it is sintered in an atmosphere of a gas contg. S and halogen such as SOCl2 or S2Cl2 mixed with an inert gas such as N2. A gas contg. S such as SO2, SO3 or other S oxide and a gas contg. halogen such as Cl2, Br2 or F2 may be used in place of the gas contg. S and halogen. The resulting sintered body is bored to form a cylindrical glass pipe and a glass capillary is obtd. by melt-spinning the pipe.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a glass capillary used in a quartz glass capillary column for chromatography.

[Prior art and its problems]

Recently, columns made of quartz glass have been used as columns for chromatography instead of stainless steel columns. This is because quartz glass columns are inert and have little interaction with the mobile phase, which allows them to separate many highly polar compounds with high resolution.

However, due to the inertness of the surface of such an excellent quartz glass column, the adhesion of the stationary phase such as methyl silicon formed on the quartz glass surface is insufficient, resulting in peeling or falling off. There was a problem that the column life was short. Furthermore, the presence of hydroxyl groups on the quartz glass surface causes a problem in that performance such as resolution deteriorates.

[Means for solving problems]

A round bar-shaped SiQ glass soot preform is grown on the end of the starting base material by the WAD method, and then this preform is sintered in the presence of a gas containing sulfur and halogen to create a base material. The above-mentioned problems were solved by boring a cylindrical base material into a cylindrical base material, and melt-spinning this cylindrical base material to form a cavity.

The present invention will be described in detail below.

First, 810,
A round bar-shaped porous preform made of glass is formed. This K is one or more multi-tube burnani, S lCe4
81 by supplying gas, O, gas, H, gas, Ar gas, etc. to cause a hydrolysis reaction and a thermal oxidation reaction in a flame.
0. A normal VAD method can be used in which fine glass powder is generated and deposited on the tip of a rotating rod-shaped base material. This porous preform is then sintered in a gas atmosphere containing sulfur and halogen. As this gas, a gas containing sulfur and a gas containing halogen, or a gas containing both sulfur and halogen is used, and the heat treatment is performed in an atmosphere where sulfur and halogen are present simultaneously. As the sulfur-containing gas, sulfur oxide gases such as SO, SO, etc. are often used because they generate SO3 groups as active groups on the surface of quartz glass. In addition, gases containing halogens mainly have a high dehydration effect (1 gas, Brl gas, F,
Gases are preferable, and gases containing sulfur and hydrogen 7 include SOCg, (thionyl chloride) gas, S*C
6*Gas, 5C14 Gas, 80, (1, Gas, 5tOs
Examples include CIl* gas, chlorosulfonic acid gas, C8cg gas, 5OBrl gas, and SFa gas. These gases are N.

After being mixed with an inert gas such as Ar or He to form a mixed gas, it is sent into the main pipe. Among the inert gases, H. is particularly suitable in terms of thermal conductivity and gas diffusion. The concentration of sulfur-containing gas in the mixed gas is 5 to 20% in the case of SO gas. If it is less than 5 mol %, sufficient active groups cannot be formed, and if it exceeds 20 mol/I/%, SO may be excessive and neutralization bubbles may remain in the sintered glass, which is disadvantageous. Further, the concentration of the gas containing halogen is 1 to 2 mol % in the case of CI gas.

If it is less than 1 mol %, a sufficient dehydroxyl group effect cannot be obtained, and if it exceeds 2 mol %, it may be excessive and may remain in the sintered glass. Sintering temperature is 150()-1700℃
810. This is the temperature at which fine glass powder melts and sinters. Further, although the time varies depending on the degree of treatment, generally about 5 to 40 minutes is sufficient.

Next, this sintered body is bored into a cylindrical glass mother tube, which is then melt-spun to form a glass capillary. Alternatively, a quartz glass tube may be jacketed onto the glass mother tube and then melt-spun.

The capillary thus obtained is made of glass containing 510t as a main component, and this glass is in a state in which hydroxyl groups have been removed and SO8 groups have been generated. This SO3
The groups are moderately distributed in the glass and contribute to improving the adhesion of stationary phases such as methyl silicon. Because sulfur and halogen are present at the same time during heat treatment, the sulfur compound effectively binds to the active residue from which the hydrogen of the hydroxyl group has been removed, resulting in efficient generation of SO1 group. be exposed.

The interior surface of this glass cavity is coated with methyl silicone while it is kept dry to form a stationary phase and used as a chromatographic column.

[Experiment example]

S10. of diameter 160mm by VAD method. A porous preform consisting of This preform was sintered at 1650° C. while flowing H gas containing 7 mol% of sO gas and 1 mol% of C6 gas.

This sintered body was perforated in the axial direction to have an outer diameter of 50 mI+I.

It is a cylindrical body with an inner diameter of 3a, and an inner diameter of 80 mm and an outer diameter of 55 mm.
After jackering a Tsuru quartz glass tube and increasing the inner diameter by melt spinning using a conventional method, the inner diameter was 200 μm.
A glass capillary with an outer diameter of 300 μm was obtained. When a mixed fragrance was analyzed using a column made of this cavity, more than 200 peaks were detected. Also, the lifespan is 3
The temperature was 5000 hours or more at 00°C.

〔Effect of the invention〕

As explained above, the method for manufacturing a glass capillary of the present invention uses 810. A glass soot is formed, this soot is sintered in the presence of a gas containing sulfur and halogen, a glass mother tube is made from this sintered glass, and this is melt-spun. The hydroxyl groups are removed from the inner surface, and active groups from sulfur compounds are generated at an appropriate concentration. Therefore, a chromatographic column made of this capillary has improved adhesion of a stationary phase such as methyl silicon, does not peel or fall off, has a long life, and exhibits high resolution.

Claims (2)

[Claims] (1) Round rod-shaped SiO is attached to the end of the starting substrate using the VAD method.
_2 A glass soot preform is grown and formed, and then this preform is sintered in the presence of a gas containing sulfur and halogen to form a base material, and this base material is bored to form a cylindrical base material. A method for manufacturing a glass capillary, characterized by melt-spinning a cylindrical base material. (2) A method for producing a glass capillary according to claim 1, characterized in that the glass tube is jacketed onto a cylindrical base material and then melt-spun.