JP2001004571A - Sample container for thermal analysis and sample filling apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sample container, for a thermal analysis, as a simple contact-type sample container, with an internal lid, which is used for the thermal analysis by a differential thermal analyzer(DTA), a thermogravimetric differential thermal analyzer(TG/DTA), a differential scanning calorimetric analyzer(DSC) or the like and which is collected and reused easily after the container is used and to obtain a sample filling apparatus which uses the container. SOLUTION: This sample container 16 for a thermal analysis is used in such a way that an internal lid 15 is brought into pressure contact with the face of a sample to be measured, This sample filling apparatus is provided with the sample container 16, for the thermal analysis, by which the internal lid 15 is brought into pressure contact with the face of the sample so as to be mounted after the sample is filled into the container 16, by which the sample is brought into contact inside the container 16 so as to be measured, by which the internal lid 15 is removed easily from a container body and by which at least the container body is reused. In addition, the sample filling apparatus is provided with a lower-part support base 18 which comprises a recessed part used to mount and hold the container. In addition, the sample filling apparatus is provided with an upper-part pestle 14 which is driven up and down in the vertical direction and by which the internal lid 15 is brought into pressure contact with the face of the sample inside the container 16.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample container for thermal analysis, and more particularly, to a simple contact type with an inner lid used for a thermal analyzer such as a differential thermal analysis, a thermogravimetric analysis, a differential scanning calorimetry, and the like. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample container for thermal analysis in which the container is collected and reused after measurement and provision, and a sample filling device used for the same.

[0002]

2. Description of the Related Art In a thermal analyzer for measuring the thermal characteristics of a material, physical and chemical changes relating to decomposition of water of crystallization, crystal transition, solid-phase reaction, etc., a differential heat for measuring a phase transition temperature and a calorific value, in particular. In an analyzer (DTA), a weight change-differential thermal analyzer (TG / DTA), a differential scanning calorimeter (DSC), a cylindrical closed or open type made of platinum or aluminum, quartz or alumina, or the like. Sample containers are commonly used.

[0003] For example, aluminum is not used for measurement of a sample containing aluminum or chlorine because it has a use limit temperature of about 500 ° C and reacts with chlorine and sodium. Platinum is not applicable to reducing substances because its limit temperature is 1500 ° C. and becomes brittle at a temperature of 1000 ° C. or higher in a reducing atmosphere or in the presence of carbon. In addition, since it reacts easily with heavy metals, it cannot be used for samples containing heavy metals. Further, it reacts with a melt such as phosphorus, arsenic, sulfur, halogen, alkali hydroxides and potassium chlorate in a high temperature range. In addition, alumina or quartz is not only expensive, but also has poor heat conduction,
It is not used for measurements that accurately detect temperatures such as transition.

[0004] Therefore, depending on the purpose of use and the type of sample, these sample containers may be used by selecting a sample container made of a predetermined material in consideration of corrosion resistance, heat resistance, thermal conductivity, cost, and the like. is important.

Therefore, for example, DTA measures the temperature difference between a sample and a reference material (usually α-alumina) as a function of temperature under a controlled temperature raising program. In addition, DSC uses a sample and a reference material (usually,
(α-alumina) under a controlled heating program to measure the difference in heat absorption between the sample and the reference material as a function of temperature.

[0006] These devices are effectively used for tracking changes in the state of a sample as a function of temperature. In connection with this change in the state, there is a flow of latent heat, such as melting, crystallization, vaporization, and sublimation. Phase transitions, chemical changes involving heat in and out,
For example, chemical changes such as oxidation, decomposition, and polymerization, as well as all thermal changes in the sample including relaxation processes such as glass transition and physical processes such as dehydration are measured.

In such a thermal analyzer, a sample container is filled with a sample, which is heated at a predetermined speed and heated, and the sample temperature is measured by a thermocouple brought into contact with the sample container.
If there is a gap between the sample container and the sample and inside the sample inside the sample container, heat transfer becomes uneven, and the sample is not heated evenly, resulting in a measurement error. Therefore, the sample
It is important to pack tightly so as not to create gaps.
For this reason, for example, as shown in FIG. 9, it is common to cover a container for filling a sample with an inner lid, and press-contact it from above to remove the gap between the sample layers for measurement.

[0008] As such an inner lid type sample container, for example, Japanese Patent Application Laid-Open No. 9-15175 discloses that a container is filled with a sample, the inner surface of the sample is covered with an inner lid 20, and after pressing, the sample container 3 FIG. 11A shows a sample container in which a notch 24 provided on one side wall is folded inward, and a lid is fixed to stably hold a sample surface. JP-A-9-33463 discloses a sample container having a two-stage diameter in which the inner diameter of the upper part of the container is smaller than the inner diameter of the lower part. A sample container is provided on the periphery to provide a claw 6 that engages with the step and presses down on the sample surface (see FIG. 11B). Japanese Patent Application Laid-Open No. Hei 9-15176 discloses that a sample container has a plurality of concave grooves on the inner surface, and after filling the sample, covers the inner lid, and after pressing, a ring 28 that freely shrinks inward is provided on the surface of the lid 22. And a sample container that is inserted into the groove so as to be engaged with the groove and holds the inner lid under the sample pressure contact [FIG.
(C)). Furthermore, Japanese Patent Publication No. Hei 7-85065 discloses an outer lid-type sample container (closed type) in which a cap-type outer lid 23 made of a material whose thermal expansion is smaller than that of the container body is covered, and the outer peripheral surface of the container body is brought into close contact. ) (See FIG. 11D).

[0009]

As described above, any of the sample containers proposed in the gazette other than the closed container in which the cap-type outer lid is covered can be filled with the sample in the container, and then the inner lid can be replaced with the sample. This is a simple closed type container that is pressed and fixed after being covered on a surface. After the pressure welding, the method of fixing (or holding) the inner lids is different, but in order to stably hold the sample in the container, these inner lids are pressed from above. The filled sample does not jump out or fall out of the container due to physical factors.

However, in all of these types of containers, complicated processing must be performed particularly on the container body, and high costs cannot be avoided as containers. Also,
In any case, it is impossible to reuse the container body. In particular, the container material is expensive, such as platinum, alumina, and quartz, and requires a manufacturing cost, for example, the material is inexpensive, the manufacturing cost is inevitably disposable like an aluminum container. What is done is very undesirable.

Usually, the sample residue after the measurement is completed is generally discarded as it is. However, if necessary, the residue is collected and used for chemical analysis, X-ray analysis or the like.
It is used effectively as the next measurement sample. However, any of the proposals in the above-mentioned publications makes it difficult to collect the residue. In addition, the sample is
A gas body that is pressed and adhered and vaporizes or decomposes and evaporates at the time of measurement, causing an increase in the internal pressure of the filled sample, and tends to not be measured at normal pressure. Furthermore, although the top lid is fixed,
It is simply a simple seal, and the gap between the inside of the container and the upper lid of the thin material is easily lifted and melted and foamed, for example, at an elevated temperature. Tend to overflow. Under such circumstances, the fine and important measuring section supporting the container is greatly damaged, and must be prevented during the measurement.

From the above, it is an object of the present invention to provide a sample container for use in a thermal analyzer, which is a simple cylindrical container having a simple shape, in which an inner lid is dropped on a sample surface and pressed as a lid, The container is easily brought into close contact with this dropping lid by pressure contact, and the internal pressure is not applied to the filled sample in the container during measurement, and stable measurement can be performed.Furthermore, after being subjected to the measurement, the residue is easily collected, It is still another object of the present invention to provide a sample container for a thermal analyzer in which at least the container body is collected and reused relatively easily and reliably.

[0013]

Means for Solving the Problems In view of the above-mentioned problems, the present inventor has made intensive studies and as a result, in order to remove the internal pressure applied to the container filled with the sample at an elevated temperature, the inner pressure of the container filled with the sample has been reduced. As a result of various studies focusing on the shape of the lid, the present inventors have found that it is possible to prevent the sample from falling out of the container, melting and foaming, and have completed the present invention.

That is, the present invention relates to a simple close-contact type thermoanalytical sample container having an inner lid over a surface of a sample to be measured.
After filling the container with the sample, the inner lid is pressed into contact with the sample surface, the filled sample in the container is pressed and adhered, and after the measurement, the inner lid is easily removed from the container body, and at least the container Provided is a sample container for thermal analysis, wherein the main body is collected and reused.

According to the present invention, for example, by using an inner lid as shown in FIG. 1, gaseous substances which are vaporized or decomposed during measurement can be easily generated from the central opening 3 or the cutout 4. As the internal pressure is not generated, the sample volume is not increased due to melting, foaming or the like unlike before. Thereby, various troubles such as the conventional simple sealed type with the inner lid fixed are not caused, and the inner lid of the sample container removed from the analyzer after the measurement is completed as shown in FIG. It is easily raised and bent along the cut by tweezers or the like.
As a result, the residue 19 can be easily taken out, and since the inner lid is not fixed, it cannot be easily removed from the container, so that the container body is not damaged or deformed at all.

Further, according to the present invention, since the sample container is a simple contact type thermal analysis sample container in which a sample container is filled with a sample and brought into close contact with the inner surface of the measurement sample surface, the sample container is shown in FIG. As described above, in the sample filling apparatus (or sealer) for filling the sample and pressing the inner lid against the sample surface, the sample container is mounted and held in the concave portion 9 of the lower support base of the sealer.
Next, the upper punch 8 is driven up and down in the vertical direction to press the inner lid against the sample surface in the container. In other words, the characteristics of the sample container according to the present invention, which is extremely simple in structure as described above, are utilized, and the filled sample can be pressed into and adhered to the container by the procedure shown in FIG.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, the sample container for thermal analysis according to the present invention has a simple, closed-bottomed cylindrical body. Taking advantage of this simple shape, the filled sample is covered with an inner lid like a drop lid of a pan,
By easily pressing the inner lid with a pestle or the like, the sample can be easily compacted and tightly filled in the container for use. In addition, the inner lid surface is a simple close-contact type thermal analysis sample container having minute holes and the like to prevent an increase in internal pressure due to gas stagnation of the filled sample.

As a result, the filled sample is prevented from increasing in internal pressure due to the vaporized components being measured, decomposition generated gas, melting and foaming, and the like. Therefore, in the conventional simple closed type,
The spilling of the sample from the container due to melting, foaming, etc., which tends to occur, is effectively prevented, and the inner lid is
Unlike the conventional simple closed type container, it can be easily removed, so that the residue can be easily recovered. As a result, the container body is also recovered without deforming the external shape or causing damage.

Therefore, an embodiment of a sample container used in the thermal analyzer according to the present invention and a method of filling the container with a sample will be described in more detail with reference to FIGS.

Therefore, the size of the sample container body is not particularly limited in the present invention, but is used for a conventionally used thermal analyzer, and preferably has an inner diameter of 5 to 7 mm. A simple cylindrical shape with a bottom having a height of about 2.5 to 5 mm is suitably used as appropriate.

Examples of the material include aluminum, platinum, alumina, quartz and the like, which are conventionally known. Therefore, in the conventional simple closed type container, its collection and reuse tended to be difficult. However, in the present invention, at least the container body is to be collected and reused as already described above. . Therefore, a container made of platinum, alumina and quartz, which is excellent in heat resistance, has a relatively high measurement temperature range, and is expensive as a material or a container, is suitably used.

Therefore, the material of the inner lid of the sample container of the present invention is usually used as a pair with the container body except for a special purpose, and may be the same material. Although the thickness depends on the material, it is preferably suitably used within a range of 10 to 200 μm.

As shown in FIG. 2, the inner lid of the present invention preferably has a central portion for exhausting various gases generated from the sample during the measurement.
900 μm or less, more preferably the lower limit is 100
An opening 3 having a size of not less than μm can be provided. Furthermore,
It is preferable to provide the cuts 4 in three directions, more preferably four directions, from the opening portion to the vicinity of the outer periphery, for example, within the vicinity of 1 mm. As a result, as shown in FIG. 10, after the measurement, the container was removed from the apparatus, and FIG.
As shown in FIG. 7, the three openings can be easily turned up along the cuts 4 with tweezers or the like. As a result, as shown in FIG. 10B, the residue 19 is easily collected without deforming or damaging the container body.

Further, on the entire surface of the inner lid according to the present invention, a plurality of fine holes can be provided as gas exhaust holes, preferably uniformly distributed over the entire surface, for the same reason as described above. This makes it possible to more effectively prevent the above-described conventional problems.

Further, the inner lid of the present invention can be provided with a circular groove 6 as shown in FIG. In the present invention, along this groove 6, for example, as shown in FIG.
A punch having a pointed jig 12 at the tip end surface of a punch rod shown in FIG. 6A is attached to the sample filling device shown in FIG. The lid can be punched. As a result, the surface can be peeled off, and the residue can be easily collected in the same manner as in the above-described example of the inner lid.

Further, as shown in FIG. 5B, the inner lid of the present invention can be provided with a columnar projection 7 at the center of the upper surface. With this projection, the inner lid can be removed from the container, for example, by pinching the projection with tweezers or the like. Also in this inner lid example, preferably, the above-described fine holes for exhaust can be provided on the entire surface.

Further, when the inner lid suitably used in the present invention has a groove as shown in FIG. 4 on the surface thereof using the above-described sample filling apparatus, after the measurement, the container is placed in FIG. The container is set in the concave portion 9 shown in FIG. 7 and the upper punch shown in FIG. 7 is pressed along this groove, whereby the inner lid is easily punched out with the ring-shaped pointed jig on the distal end surface. As a result, the residue can be easily collected.

When the inner lid is provided with, for example, a cylindrical connector handle as shown in FIG. 5 as described above, it is preferable to use this sample filling device to fill a sample. As shown in FIG. 8, a punch having a concave portion for accommodating a cylindrical handle provided on the lid is preferably used in a central portion of the tip surface of the upper punch as shown in FIG. Thus, even when such an inner lid is used, the sample can be closely packed in the container by pressing the inner lid similarly.

The sample container according to the present invention can be appropriately used as a sample container for a conventionally known thermal analyzer without any particular limitation.
For example, conventionally, in the case of a thermal analyzer, although it depends on the sample to be sampled, the sample content usually falls outside the sample container of the balance beam due to decomposition of the measurement sample, rapid reaction, melting / foaming, etc. which occur during measurement. It is common for objects to overflow or to fall.

However, even if such a situation occurs during the measurement, it cannot be confirmed or dealt with during the measurement, and no measure can be taken until the measurement is continued and completed. . Therefore, the fused or fixed sample causes a great deal of damage to the periphery of the apparatus supporting the sample container, the heating furnace, and the like. Therefore, for example, in the thermal analyzer described below, in order to prevent these troubles beforehand, monitoring and warning can be instructed from outside in such a situation. by this,
Under such circumstances, the simultaneous thermogravimetric / differential thermometer (TG) capable of automatically stopping the measurement as necessary.
/ DTA).

The sample container according to the present invention described above can be suitably used as a sample container for such a thermal analyzer. That is, this thermal analyzer
During the measurement, it is possible to simultaneously detect changes in the temperature and the weight difference between the sample and the reference, which are related to changes in the sample.
Usually, the sample and the container to fill the reference are adjacent,
Each is mounted on a support member, and sensors and the like for detecting these temperature changes and weight changes are mounted inside, and the whole of these is unitized in a heating (or cooling) container,
Moreover, these functions are controlled by the microcomputer.

Therefore, in order to monitor the above-mentioned troubles, a portion where the state of the sample container portion inside the heating container (furnace) can be confirmed, that is, at a position higher than the balance beam, with heat resistance and corrosion resistance, An opening window provided with a transparent alumina plate is provided. Through this opening window, it is possible to visually observe or automatically monitor as necessary as follows. As a means, for example,
A CCD camera can be attached to the opening. With this camera, the photographed and imaged state can be displayed and observed. Also, always compare the sample weight given before measurement with the thermogravimetric measurement value obtained during measurement.
A microcomputer having a control function can be mounted. In addition, a position detector for detecting the overflow or fall of the sample from the sample container is installed in the heating furnace, the condition is monitored, and the result is displayed.

Further, in conjunction with the detection obtained as described above, for example, when the image of the CCD camera is recognized by the image recognition software for the above-mentioned situation change such as the movement or drop of the sample, or by the position detector. If the difference between the weight of the sample before measurement and the thermogravimetric value obtained during the measurement becomes negative when the recognition is made, a warning sound is emitted from the built-in speaker of the microcomputer and the measurement is stopped by the control unit. The above-mentioned instruction can be issued to automatically stop the temperature rise of the heating furnace, thereby preventing the above-described trouble at the initial stage.

Therefore, in such a TG / DTA apparatus, the sample container according to the present invention is suitably and suitably used. Since the above-described effects due to the sample container situation are similarly exhibited, there is no obstacle to the safety measures provided by this thermal analyzer. Further, the use of the sample container according to the present invention can prevent the above-mentioned troubles at an early stage, since the safety measures provided by this measuring device are more reliably implemented than using the conventional container. In addition, the safety measures can more reliably ensure stable measurement because they can be further reduced.

[0035]

According to the present invention, there is provided a sample container having a simple structure in which an inner lid is placed over a cylindrical container body and physically pressed against the inner lid, and the inner lid is a simple flat plate. The sample can be easily brought into close contact with the container, and the inner lid can be pressed against the container. As a result, the preparation of the sample is significantly easier than before, and the preparation time is significantly reduced.

Further, since the inner lid is provided with openings, cuts, fine holes, pointed grooves, and the like, the internal pressure increases due to gaseous substances that evaporate or decompose and evaporate during measurement, as in the prior art.
Melting and foaming can be prevented. As a result, an increase in the filling volume caused by these factors is caused, and troubles such as overflowing of the contents to the outside of the container or falling are effectively prevented. This effectively prevents the conventional trouble of damaging the container support and the inside of the furnace due to melting and sticking around the container.

Also, a notch or a pointed groove is formed on the inner lid (along the groove, punched out with a pointed jig after measurement).
Also, by applying a handle, etc., the inner lid can be removed from the container body after measurement without causing any damage or deformation to the container body, so that the residue can be easily collected, and if necessary The residue is effectively used as a secondary measurement sample for chemical analysis or X-ray analysis.

Furthermore, since the inner lid can be detached without damaging the container body and the container body can be easily recovered as described above, it has been impossible to reuse it in the past. It is possible to provide a sample container for thermal analysis that can collect and reuse a container body made of a material such as platinum, alumina, and quartz.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a sample container.

FIG. 2 is an example of the inner lid of the sample container of the present invention.

FIG. 3 is another example of the inner lid of the sample container of the present invention.

FIG. 4 is another example of the inner lid of the sample container of the present invention.

FIG. 5 is another example of the inner lid of the sample container of the present invention.

FIG. 6 is a conceptual side view of a sample filling device used in the present invention.

FIG. 7 is a view showing an upper punch having a ring-shaped pointed portion on a distal end surface.

FIG. 8 is a view showing an upper punch having a cylindrical concave portion on a distal end surface.

FIG. 9 is a view showing a step of pressing and filling a sample into a sample container.

FIG. 10 is a conceptual diagram showing an embodiment using a sample container according to the present invention.

FIG. 11 is a diagram showing an example of press-contact filling of a sample using a conventional sample container.

[Explanation of symbols]

 1, 15, 20, 21, 22, 25 Inner lid 2, 16 Sample container body (bottomed cylindrical shape) 3 Opening 4 Notch 5 Micro hole 6 Pointed groove 7 Projection 8, 14 Upper punch 9, 18 Lower support 10 Set screw 11 Handle 12 Ring-shaped point 13 Cylindrical recess 17 Sample 19 residue 23 Cap-type lid (outer lid) 24 Notch 26 Upper part of container 27 Lower part of container 28 Ring stopper

Claims (10)

[Claims] 1. A simple close contact type thermal analysis sample container in which an inner lid is placed over a surface of a sample to be measured. After the sample is filled in the container, the inner lid is pressed into contact with the sample surface, and the inner lid is A sample container for thermal analysis, wherein the inner lid is easily removed from the container body after the filled sample is brought into close contact with the container, and at least the container body is collected and reused. 2. The sample container for thermal analysis according to claim 1, wherein the container body is a bottomed cylindrical shape having an inner diameter of 5 to 7 mm and a height of 2.5 to 5 mm. 3. The sample container for thermal analysis according to claim 1, wherein said inner lid has a thickness of 10 to 200 μm. 4. The inner lid has a central part at 50-90.
The thermal analysis sample container according to claim 1, wherein the sample container for thermal analysis has an opening of 0 μm and cuts in at least three directions from the opening portion to the vicinity of the outer periphery. 5. The sample container for thermal analysis according to claim 1, wherein a large number of fine holes are provided on the entire surface of the inner lid. 6. The sample container for thermal analysis according to claim 5, wherein the inner lid has a circular groove punched by a pointed jig on an inner surface near an outer peripheral edge thereof. 7. The sample container for thermal analysis according to claim 5, wherein the inner lid has a columnar projection at the center of the upper surface. 8. A sample filling apparatus (or sealer) for filling a sample into a simple close-contact type thermal analysis sample container having an inner lid over a measurement sample surface and pressing the inner lid against the sample surface. A sealer having a lower support base having a concave portion for mounting and holding the sample container, and an upper punch for vertically driving the inner cover to press the inner lid against a sample surface in the container. Sample filling device for sample containers for thermal analysis. 9. The sample filling apparatus according to claim 8, wherein a ring-shaped pointed jig is provided on a tip end surface of the upper punch. 10. The sample filling apparatus according to claim 8, wherein the upper punch has a cylindrical concave portion at a central portion of a tip surface thereof.