JPS5968654A - Glass bead preparing vessel - Google Patents

Abstract

PURPOSE:To improve the durability and prevent the peelability or the like even in caes of the repeated use, by forming a preparing vessel with a sintered material consisting essentially of silicon carbide, silicon nitride, or sialon. CONSTITUTION:When the preparing vessel consists essentially of silicon carbide, it is sintered by the pressure sintering method, or an easy sintering powder is produced by the raw material powder method and a sintering auxiliary is added to sinter it by the normal-pressure sintering method. When the preparing vessel consists essentially of silicon nitride, MgO, Mg3Nz, or the like is added as an auxiliary improving sintering efficiency. When the preparing vessel consists essentially of sialon, one or more of Mg, Ca, Y, Nd, and Er and combined as M of Mx (M is a metal having an electronegativity of 1.0-1.2 and x<=2) and are sintered by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION 1 The present invention relates to a glass bead preparation container used for fluorescence X-ray analysis, and has improved peelability and durability.

■ In general, sample preparation for fluorescence X-ray analysis depends on the state of the substance, the content of the target element, the form of its existence, etc.
method, powder molding method, melting method, solution method, precipitation method,
This is done using methods such as ashing.

Analytical samples of various raw materials and products in the field of ceramics are often prepared by press-molding finely pulverized materials. This powder method produces 11 uniform samples! Since it is difficult to mold a certain shape, there is a problem that the fluorescent X-ray intensity varies widely even within the same original sample, resulting in low analytical accuracy.

The melting method (glass bead) method involves melting a finely ground original sample together with a vitrification flux in a container to prepare a measurement sample in a glass state with relatively good moldability. This glass bead method has the advantage of increasing the uniformity of the sample and reducing errors due to mineral composition, which is a major drawback of the powder method, so it is a sample preparation method with high analytical accuracy and reproducibility. It is often used in relatively large numbers.

Containers for preparing glass beads are generally required to have heat resistance near or above the melting point of the sample, thermal shock resistance, non-reactivity of the sample, peelability so that the glass can be easily separated from the container, and durability against repeated use. I can vomit.

Currently, many glass bead preparation containers are made of platinum or platinum alloys. manufactured products are used. However, conventional platinum-based containers such as kone have low durability, and when used repeatedly, they have the disadvantage that peelability and moldability deteriorate due to rapid heating and cooling. For example, using a container made of gold-platinum alloy, cement raw materials are mixed with lithium tetraborate as a flux.
If the operation of melting at 200° C. and preparing a glass bead sample is repeated, the surface of the container will gradually become rough, making it difficult to peel off the sample, and the sample may even break. If the sample preparation is further repeated 200 to 300 times, the container deteriorates to the extent that polishing ff is required, and if the sample preparation is repeated 600 to 800 times, it deteriorates to the extent that recasting is required.

One way to improve the peelability is to change the surface tension of the molten sample by spraying a similar molecular gas containing halogen into the container, but with this method, the center of the sample bulges, making it difficult to form the bead. Furthermore, methods using various stripping agents have the disadvantage that the dilution ratio becomes large and interference with coexisting elements occurs, and improvement in stripping properties has not been sufficiently achieved.

In this way, when conventional glass bead preparation containers are used for cement analysis, their durability is low, and removability deteriorates when used repeatedly. When this was done, the glass bead method was not used and the powder method was used. Therefore, continuous automatic light
In the line analysis, the analysis'M degree was low and stable analysis results could not be obtained.

The present invention solves these problems and provides a glass bead preparation container that is highly durable and does not lose its peelability even after repeated use, and allows continuous glass bead method analysis in the analysis of cement raw materials. The object of the present invention is to make it possible to carry out this process, and its structure is characterized by being made of a sintered body whose main material is silicon carbide, silicon nitride, or sialon.

The present invention will be explained in detail below.

The glass bead preparation container according to the present invention is made of a sintered body of silicon carbide, silicon nitride, or sialon, and a small amount of a sintering aid shade is added for convenience of the sintering process.

Here, the cases of each of the above compositions will be explained.

■ When using silicon carbide as the main material, it is difficult to sinter silicon carbide Vi, so it may be sintered by the additive sintering method, or it may be possible to create a powder that is easy to sinter by changing the manufacturing method and processing method of the raw material powder. A high-density product can be obtained by adding a sintering aid and sintering by pressureless sintering. The preparation container mainly made of silicon carbide produced in this way has excellent removability and durability.

(2) When using silicon nitride as the main material, it is recommended to add MfO, M23Nz, Y2O3, YN, etc. as an auxiliary agent to improve sinterability. Recently, a method that does not use a sintering aid has also been proposed, and it is also possible to manufacture by such a method.

The silicon nitride-based preparation container manufactured in this way has particularly good thermal stability and has a smooth surface, so no bead cracking occurs even when used with the edges turned over.1) Peelability and durability Good properties.

Ni\4ToJ-rPl+lL-kftonasu 廿Iaron is a general term for Si-AM-0-N-based compounds, and has the general formula S1H-2Affiz oZN, -7 (z=0
~4.2) β-8i*N4 solid solution (β-
sialon), various AtN pseudopolytype solid solutions, and (Os
There is an α-sialon expressed as N)ts (M is a metal with an electronegativity of 1.0 to 1.2, X≦2). In the case of α-sialon, M is My, Ca, Y, N
It is manufactured by combining one or more of the metals d and Er and heating and sintering the combination.

The preparation container manufactured in this way, which is mainly made of Sialon, has a small coefficient of thermal expansion and excellent dimensional stability, has a smooth surface, has good peelability, and has excellent durability without change even after repeated use.

As described above, the glass bead preparation container according to the present invention has good heat resistance and thermal shock resistance, excellent sample peelability, and is several times more durable than conventional containers mainly made of platinum or gold-platinum alloy. N: These properties do not deteriorate even after repeated use.

For example, when analyzing cement raw materials, compared to conventional materials made of gold-platinum alloys, which require polishing because their releasability decreases after repeated use of 200 to 300 times and cracks form in the beads. Therefore, in the preparation container of the present invention, 1
Even after repeated use over 500 times, the removability remains unchanged.
No changes were observed in the container itself.

Further, the preparation container according to the present invention can be manufactured by producing a sintered body by a high-pressure sintering method using solid compression, a hot isostatic pressure sintering method, etc., and cutting and molding the sintered body into a desired shape. .

When preparing an analytical sample using the preparation container of the present invention manufactured as described above, a conventional set of heating blades such as high frequency heating, gas burner heating, resistance furnace heating, etc. can be used as the heating method.

Next, examples will be shown.

1 Example 1) β-8iC powder (average particle size 07μ
) A 100 M solution containing 1 part by weight of I14 C as a sintering aid was heated to 2000° C. by high-frequency induction in graphite under uniaxial pressure of 300 kg/cIl.

The specific gravity of the obtained sintered body was 112.6.

This sintered body was cut and molded into a cylindrical container with an outer diameter of 50+ m, an inner diameter of 40 mm, a height of 40 mm, and a wall thickness of 5 m+ to produce a glass bead preparation container.

This container can be used to add NaJ as a flux to cement raw materials.
40y was added and heated in an electric furnace at 1200°C for 5 minutes.
A sample in a glass state was prepared. 1500 under the same usage conditions
Although glass beads were prepared repeatedly, there was no change in moldability and releasability, and no changes were observed in the container itself.

As a comparative example, glass beads were repeatedly prepared by adding the same flux as in Example 1 and high-frequency heating under the same conditions using a gold-platinum alloy container containing 5% gold.
Gradually, the surface of the container became rough, the removability deteriorated, and the beads began to crack, and after about 230 times, the container deteriorated to the point where it had to be polished.

Example 2) A pressure-molded material of α-8i 3 N4 was calcined at 1420° C. in a vacuum, placed in a BN capsule, and vacuum-sealed in quartz glass.

This sealed sample was further vacuum sealed in Pyrex glass to obtain a double sealed sample. This sample was placed in a high-pressure furnace of a HIP device, and argon gas was used as the pressure transmission medium.
A sintered body was produced by processing at 1500° C. under a pressure of Pa.

This sintered body was cut and molded into a cylindrical container with an outer diameter of 50 m, an inner diameter of 40 m, a depth of 20 m, and a wall thickness of 5 cm to produce a glass bead preparation container.

1 °°8″″″1″ (+71:/ ) W″″
l'Mlfl:LiL2L i z B407 was added and heated at 1200° C. for 5 minutes to prepare glass beads. It was repeated over 1,500 times under the same conditions, but the surface was smooth and peelable, and no deterioration was observed.

￥Example 3) The composition of the sintered body is Mfo-* (Sie, sM
x-t) (Oo-sf N15-+) using S' s N4+ AX N + M y O as a raw material 1 □11. □, )-7-/L-7#:
1-Af7111, crushed and mixed in a bot mill made of furnace alumina. This powder was placed in a graphite die with an inner diameter of 50 mm for 2
It was pressurized to 0 MPa and ignited at 1800°C under N2 atmosphere.

The sintered body was confirmed to be α-sialon having an α-3S sN4 type structure by powder XIR diffraction.

This sintered body has an outer diameter of 50 mm, an inner diameter of 40 mm, a depth of 20 m+,
A glass bead adjustment container was manufactured by cutting and molding a cylindrical container with a wall thickness of 5 strips.

When glass beads were prepared using this container by a high-frequency heating method, no change was observed in the releasability of the beads or in the container itself even after repeated use 1700 times.

As explained above in detail based on the examples, the glass bead preparation container according to the present invention has good heat resistance and thermal shock resistance, good peelability from sample glass beads, and durability against repeated use. I'm especially good at sex. Therefore, according to the present invention, automatic continuous bright light X#3 using the cement raw material melting method! Analysis is now possible.

Claims (1)

[Claims] glass bead preparation container Mainly silicon carbide, silicon nitride or sialon Garai characterized by being composed of a sintered body as a phase. Speed preparation container. Mail