WO2007114317A1

WO2007114317A1 - Peltier device and temperature regulating container equipped with the peltier device

Info

Publication number: WO2007114317A1
Application number: PCT/JP2007/057034
Authority: WO
Inventors: Tetsuaki Nishida; Kenichi Kobayashi; Akira Morishige; Kazumi Manabe
Original assignee: Kitakyushu Foundation For The Advancement Of Industry, Science And Technology
Priority date: 2006-03-31
Filing date: 2007-03-30
Publication date: 2007-10-11
Also published as: JP5024835B2; US20090241554A1; JPWO2007114317A1

Abstract

There is provided, by using a conductive glass consisting primarily of a salt of vanadic acid as an electrode, a Peltier device capable of maintaining a constant temperature at a high accuracy, excellent in handleability, easy to regulate temperature and excellent in the stability of cooling performance, capable of reliably preventing electrode corrosion caused by chemicals and dew condensation, and excellent in the reliability and durability of the electrode. The Peltier device has a heat absorbing portion and a heat emitting portion, and at least the electrode of the heat absorbing portion is formed of a conductive glass consisting primarily of a salt of vanadic acid.

Description

Peltier soot element and temperature control container provided with the same

Technical field

[0001] The present invention relates to the research field of peltier elements and biotechnology that are easy to adjust temperature and excellent in handleability, and is used for observation and manipulation of tissues and cells in a living body and in the pharmaceutical field. This is related to a temperature control vessel equipped with a Peltier element that can optimally control the temperature of the specimen when performing microscope observation and microscope operation while controlling the temperature of the specimen in quality control and material testing in the industrial field. is there.

Background art

[0002] Conventionally, in a temperature control system for culturing used in the fields of biotechnology and medicine, a method of changing the temperature of a medium such as antifreeze or water and circulating it around a specimen using a pump, The method used to change the temperature and control the temperature by changing the polarity of the cooling module. In the method of circulating with a pump by changing the temperature of the medium, the circulation path of the medium has to be kept warm, the apparatus becomes large, temperature difference is likely to occur during circulation, lacks responsiveness to heating and cooling, and high There was a problem that it was difficult to obtain temperature accuracy.

The method of changing the temperature and controlling the temperature by changing the polarity of the cooling module has the problem that it lacks long life and reliability as a device that causes significant damage to the cooling module.

Both methods can heat and cool multiple culture vessels at the same time, but can individually heat and cool containers with fine storage spaces, or culture vessels with multiple cells on a cell-by-cell basis. However, it cannot be heated and cooled selectively, and there is a problem that it lacks versatility.

In addition, (Patent Document 1) states that “a cell cultured in a culture vessel using a temperature-responsive polymer compound as a cell culture substrate is higher than the boundary point at which the temperature-responsive polymer compound starts to precipitate from water. While observing with a microscope at a temperature, the cooling fluid is added until the temperature-responsive polymer compound in the observation field reaches a temperature lower than the critical point without blocking the optical path of the transmitted light. Disclosed is a method for selecting cultured cells using a temperature-responsive polymer compound, wherein only desired cells or cell masses are selected by spraying and cooling, and the cells are detached and recovered from the container. Yes.

(Patent Document 2) states that “a glass plate for heating having a heater function in which electrodes for an anode and a cathode are attached so as to face each other at the periphery of a transparent glass formed by vacuum deposition of a transparent conductive film; An apparatus for heating and cooling combined with one or a plurality of cooling modules using the Peltier effect is disclosed.

Patent Document 1: JP 2003-102466 A

Patent Document 1: Japanese Patent Laid-Open No. 9-122507

Disclosure of the invention

Problems to be solved by the invention

[0003] However, the above-mentioned conventional technology has had the following problems.

(1) The method for selecting cultured cells of (Patent Document 1) includes a heating surface on which a culture vessel is placed and the bottom surface is heated, a small-range light transmitting hole opened at the center of the heating surface, and the hole. It is possible to cool only a narrow range by providing a discharge port that blows a cooling fluid toward the bottom of the culture vessel facing the cell. The purpose is to recover, and the minute space cannot be heated and cooled to an arbitrary temperature, and the use is limited to the selection of cultured cells.

(2) The heating / cooling combined device of (Patent Document 2) is formed of hard glass, so that it is difficult to finely process and lacks shape flexibility, and forms a fine space for storing chemicals and aqueous solutions. In other words, it has a problem of lack of handleability and versatility.

[0004] The present invention solves the above-described problems. By using a conductive glass mainly composed of vanadate as an electrode, a constant temperature can be accurately maintained, and the temperature can be easily adjusted. ! / Providing excellent Peltier elements and easy processing of the container body, excellent shape flexibility, forming a fine space to accommodate chemicals and aqueous solutions, and excellent chemical resistance and storage stability At the same time, a minute space containing chemicals and aqueous solutions can be efficiently heated and cooled to stably hold it at any temperature for observation and various measurements. The purpose of the present invention is to provide a temperature-controlled container equipped with a Peltier element that is excellent in reliability, versatility, and workability.

Means for solving the problem

[0005] In order to solve the above problems, a Peltier device of the present invention and a temperature control container including the Peltier device have the following configurations.

The Peltier element according to claim 1 of the present invention is a Peltier element having a heat absorption part and a heat generation part, and is formed of a conductive glass mainly composed of at least the electrode force vanadate of the heat absorption part. It has the structure which is.

This configuration has the following effects.

(1) By forming the endothermic electrode with conductive glass mainly composed of vanadate, it is possible to cool the object with a gradual temperature change. It can be held well and has excellent cooling temperature stability.

(2) By forming the electrode with conductive glass whose main component is vanadate, corrosion of the electrode due to chemicals or dew condensation can be surely prevented, and the reliability and durability of the electrode are excellent.

[0006] Here, as the conductive glass (vanadate glass) mainly composed of vanadate, vanadium oxide, alkali metal oxides such as diphosphorus pentoxide, potassium oxide and sodium oxide, oxidation It is possible to use an alkaline earth acid such as barium, vitrified acid cerium, tin oxide, lead oxide, copper oxide, etc.

This conductive glass is obtained by vitrifying a vanadium-containing composition to produce an acid glass, and subjecting the acid glass to an annealing treatment not lower than the glass transition temperature of the acid glass and not higher than the melting point. And a reheating step of maintaining the temperature in a temperature region, preferably a temperature range of not less than the crystallization temperature of the acid glass and not higher than the melting point, for a predetermined time.

[0007] The crystallization temperature and melting point can be determined by actually measuring an oxide glass by differential thermal analysis (DTA), differential scanning calorimetry (DSC), or the like. It can also be obtained by performing a thermodynamic calculation using the estimated component phase diagram.

When the crystallization temperature is determined by differential thermal analysis (DTA), the temperature at the center point of the exothermic peak of crystallization or the temperature at the high-side station temperature is used as the crystallization temperature. Differential heat content When determining the melting point by analysis (DTA), the temperature at the center point of the endothermic peak above the crystallization temperature is taken as the melting point.

[0008] As a means for vitrifying the composition in the vitrification step, a composition such as a mixture of crystalline solids is changed to a liquid or a gas, and then is crystallized without being crystallized. There is no particular limitation as long as the glass can be made. For example, an oxide glass can be obtained by heating and melting a composition such as a mixture of crystalline solids and then rapidly cooling the composition. Alternatively, an oxide glass can be obtained by once vaporizing a composition such as a mixture of crystalline solids by vapor deposition, sputtering, glow discharge, or the like. Further, an oxide glass can also be obtained by passing through a gel such as a sol-gel method.

[0009] As a means for maintaining the temperature range between the glass transition temperature or the crystallization temperature and the melting point or less during the reheating step of the acid oxide glass, for example, an electric furnace or the like is set to the reheating temperature in advance. When the temperature inside the furnace becomes constant after setting, the acid glass is put into the furnace, and when the target time has elapsed, the electric furnace isotropic acid glass is taken out and air, water, Cooled with a member such as a fluid such as ice water, a cooled copper plate or stainless steel plate, or a roller made of copper or stainless steel. Alternatively, after reheating the above oxide glass in a furnace such as an electric furnace for a certain period of time, the temperature in the furnace is gradually lowered or the heating source power in the furnace is gradually moved away to place the oxide glass in the furnace. What is allowed to cool in is used. The inside of the furnace for reheating can be an inert gas atmosphere such as air, nitrogen, or argon.

[0010] The holding time in the reheating step can be appropriately set to an optimal time so that the electric conductivity of the oxide glass that has undergone the reheating step is increased. The holding time varies depending on the composition of oxide glass, heat capacity, and reheating temperature, but is set to, for example, 1 to 180 minutes. When the holding time is shorter than 1 minute, the thermal energy given to the oxide glass is small, so the rate of increase in electrical conductivity is small and the rate of increase is uneven. Since the electrical conductivity may decrease due to precipitation or melting, and the productivity decreases, the deviation is also preferable.

[0011] When the heating temperature in the reheating step is equal to or lower than the crystallization temperature of the acid glass, the thermal energy given to the acid glass is small, so the rate of increase in electrical conductivity is small. There is a tendency that variations tend to occur. Also, during the reheating process If the thermal temperature falls below the glass transition temperature of the acid glass, the distortion of the glass skeleton cannot be removed, and the active energy (band gap) for electron hopping cannot be reduced. It is difficult to increase the electrical conductivity, and if the heating temperature is higher than the melting point of the acid glass, the melting of the oxide glass and the precipitation of crystals are promoted and the electrical conductivity is lowered. Absent.

The electrical conductivity at 25 ° C at room temperature of the oxide glass (conducting glass) is, for example, by applying a silver paste to a glass piece with a thickness of lmm or less, drying it, and then using silver-containing solder. An electrode is formed and can be obtained by a DC two-terminal method or a DC four-terminal method.

[0012] The electrical conductivity at 25 ° C reheating step prior to the Sani匕物glass (conductive ^{^{glass), 10_ 8 ~10 _4 S '}} cm _ 1 preferably 10 ^_6 ~10 ^_4 S' range cm ^_1 It is preferable that it exists in. Electric conductivity Shirubedo is 10 ^_6 S 'as the lower than cm- ^1, tends to become difficult to improve the electrical conductivity even after re-heating step to a practical level was observed, 10 ^_8 S' less than cm ^_1 This is not preferable because this tendency becomes remarkable. Increasing the electrical conductivity of the acid glass before the reheating process to more than 10 ^_4 S 'cm- ¹ is limited by the composition of the glass oxide and the temperature history of the vitrification process, resulting in poor productivity. At the same time, production stability is lacking, which is not preferable.

The electric conductivity of the oxide glass which has passed through the reheating step (conductive glass), 'is cm- ¹ preferably 10 one ³ ~ lS' 10 one ⁴ ~ lS and have your room temperature of 25 ° C increase the range of cm- ¹ Can be made. As the electrical conductivity becomes smaller than 10 cm · cm- ¹ , when conductive glass is applied to the electrodes of a Peltier element, there is a tendency that power consumption increases and lacks energy saving. In particular, it is not preferable that the electric conductivity is smaller than 10 ^_4 S 'cm ^_1 because this tendency becomes remarkable.

[0013] In particular, the conductive glass was reheated by holding the acidic glass obtained by vitrifying the composition containing vanadium for a predetermined time in a temperature range above the crystallization temperature of the acidic glass and below the melting point. If it is, it is possible to produce conductive glass having a high electrical conductivity of 10 ^_1 S'cm— ¹ or more at room temperature by distributing electrons in the oxide glass to high energy levels, The electrical conductivity can be dramatically increased just by holding it for a short period of about 30 minutes in the specified temperature range, and even if the holding time in the specified temperature range varies, there is little fluctuation in the electrical conductivity. Remarkably excellent in production stability. In addition, by changing the heating time, holding time, etc. in the reheating process, the electrical conductivity of the conductive glass at room temperature should be designed and controlled accurately in the region of 10 ^{_4 S'cm} ^{_ 1} or more. Can increase product yield.

[0014] The conductive glass contains additives such as Agl, Nal, Ag, Ag0, InO, SnO, and SnO.

2 2 3 2

Even if it ’s scented. This is because the electrical conductivity can be increased by the effect of the additive. In addition to Agl, Nal, Ag, etc., a reduction inhibitor such as CeO may be added. This

2

This prevents the additives such as Agl, Nal and Ag from being reduced and maintains high electrical conductivity.

[0015] In addition, vanadium oxide (V O), barium oxide (BaO), and iron oxide (Fe

twenty five

O) vanadium oxide in the three-component system of (VO) is from 40 to 98 mole ^_0/0 preferably 60

2 3 2 5

85 mol% is preferred. As it becomes less than 60 mol%, it tends to be difficult to maintain a glass skeleton with vanadium as the main skeleton, and it becomes difficult to obtain high electrical conductivity. In particular, since the content of subcomponents is reduced, adjustment functions such as electrical conductivity and mechanical properties due to the subcomponents tend to be reduced. In particular, if the amount is less than 40 mol% or more than 98%, these tendencies are remarkable, which is not preferable.

The barium oxide (BaO) in the above three-component system in the oxide glass is 1 to 40 mol%, preferably 10 to 30 mol%. When the amount is less than 10 mol%, homogenous vitrification tends to be difficult, and when the amount is more than 30 mol%, the mechanical strength decreases and the glass tends to become difficult to form. In particular, when the force is less than 1 mol% and the amount is more than 40 mol%, these tendencies tend to be remarkable, and therefore the deviation is also preferable.

Acid iron iron (Fe 2 O 3) in the above three-component system in the acid glass is preferably 1 to 20 mol%

twenty three

Is preferably 5 to 20 mol%. As the content becomes less than 5 mol%, the contribution to the electron hopping due to the valence electrons of iron tends to be reduced, and the electrical conductivity tends to be difficult to improve. .

In particular, the molar ratio of vanadium oxide (V O), barium oxide (BaO), and iron oxide (Fe O)

2 5 2 3

, Respectively 60 to 85 Monore ^_0/0, 10-30 Monore ^_0/0, to be in the range of 5 to 20 Monore ^_0/0, by reheating the Sani匕物glass, the number of electrical conductivity at room temperature Raise by more than an order of magnitude 1 0 ^{_ 1} S ′ cm— ¹ or more, and excellent characteristics as a heating element and various electrode materials can be exhibited.

[0016] The thickness of the conductive glass used as the electrode of the Peltier element is 0.1 nm! ~ 5mm is preferred. As the thickness of the conductive glass becomes thinner than 0.1 mm, the strength of the electrode decreases and the electrical conductivity tends to decrease. As the thickness becomes thicker than 5 mm, the resistance increases and temperature control becomes difficult. Both are not preferred.

[0017] A temperature control container according to claim 2 of the present invention has a configuration including a container body and the Peltier element according to claim 1 disposed on the bottom or side of the container body. do it! / Speak. With this configuration, in addition to the operation of claim 1, the following operation is provided.

(1) By having a Peltier element arranged on the bottom or side of the container body, temperature adjustment is easy and cooling efficiency and reliability are excellent, and the container body and Peltier element can be handled as a unit. It is possible and is excellent in handling, performance and space saving.

[0018] Here, the conductive glass serving as the electrode of the heat absorbing portion of the Peltier element is disposed so as to be in contact with the bottom or side of the container body. The container body is not affected by the chemical solution or solution contained in the interior, and is formed of a material having heat transfer properties that can cool the chemical solution or solution contained in the interior by contacting the heat absorbing portion of the Peltier element. Good. For example, glass such as quartz glass or hard synthetic resin is preferably used. Further, the container body can be partially or entirely formed of conductive glass. When part of the container body is formed of conductive glass, part or the whole of the bottom part or side part is formed of conductive glass, and the container body is formed by pasting it with quartz glass or synthetic resin. However, conductive glass may be bonded or formed on the outer surface of the inner wall portion formed of the above-described quartz glass or synthetic resin.

Since the conductive glass can be finely processed by a focused ion beam cage or the like, it can be easily processed according to the shape of a part or the whole of the container body, and is excellent in productivity.

[0019] The invention according to claim 3 is the temperature control container according to claim 2, wherein at least a part of the container body is formed of the conductive glass.

With this configuration, in addition to the operation of the second aspect, the following operation is provided. (1) By forming at least a part of the container body with conductive glass, the thermal conductivity and chemical resistance can be improved, and various chemicals and solutions can be stored and heated efficiently with heating means and Peltier elements. Can be cooled, and has excellent versatility and reliability.

(2) By forming the container body with conductive glass, it is possible to perform fine processing using a processing method such as a focused ion beam, which is excellent in shape flexibility and easy to downsize the container body, saving space. Excellent in properties.

[0020] Here, when a part of the container body is formed of conductive glass, in particular, heating is performed by forming at least a part of the bottom part or the side part heated or cooled by a heating means or a Peltier element with conductive glass. The heat can be efficiently transferred between the means and the Peltier element and the chemical solution or solution contained in the container body, and the heating and cooling efficiency is excellent.

As the heating means, one using a heat generating resistor or the like that can selectively heat the container body is suitably used. By disposing one or more heating means and Peltier elements on the bottom or side of the container body, heating and cooling can be performed easily.

It is preferable to install a temperature sensor such as a thermocouple on the container body. The temperature sensor measures the temperature of the container body or the chemical solution or solution contained in the container body, and based on the measured value, the controller controls the drive of the heating means and Peltier element, so that any temperature can be obtained. Can be held with high accuracy.

The conductive glass forming the container body is the same as the conductive glass forming the electrode of the Peltier element.

[0021] The invention according to claim 4 is the temperature regulating container according to claim 3, wherein the electrode of the heat absorbing portion of the Peltier element forms at least a part of the container body. Having a configuration that is electric glass! /

With this configuration, in addition to the operation of the third aspect, the following operation is provided.

(1) Since the electrode of the heat absorption part of the Peltier element is a conductive glass that forms at least a part of the container body, the container body and the Peltier element can be easily integrated, and a minute container body can be formed. It can be reliably cooled, and it can reliably prevent corrosion of the electrode due to chemicals and condensation, and the Peltier element has excellent reliability and durability.

Here, the conductive glass serving as the electrode of the heat absorption part of the Peltier element is at least one of the container body. However, the inner wall portion may be formed of the above-mentioned quartz glass or synthetic resin, and the outer surface thereof may be formed on the outer surface. It may be stacked. In particular, the conductive glass power used as the electrode of the heat absorption part of the Peltier element is directly in contact with the chemical solution or solution contained in the container body, which is superior in cooling efficiency and chemical resistance of the container body. It can improve the storage stability of various solutions, and has excellent durability and long life.

[0022] The invention according to claim 5 is the temperature control container according to any one of claims 2 to 4, further comprising heating means disposed on the bottom or side of the container body. It has a configuration characterized by this.

With this configuration, in addition to the operation of any one of claims 2 to 4, the following operation is provided.

(1) By having the heating means arranged at the bottom or side of the container body, it is excellent in heating efficiency and reliability, and it is possible to handle the container body and the heating means integrally. Excellent in performance and space saving.

(2) By having both the Peltier element and the heating means in the container body, the container body can be adjusted to a desired temperature in a short time, and is excellent in versatility and handling.

Here, as the heating means, one using the above-described heating resistor or the like is preferably used.

[0023] The invention according to claim 6 is the temperature regulating container according to claim 5, wherein the heating resistor of the heating means is the conductive glass forming at least a part of the container body. Have a success.

With this configuration, in addition to the operation of the fifth aspect, the following operation is provided.

(1) Since the heating resistor of the heating means is a conductive glass that forms at least a part of the container body, the container body and the heating means can be easily integrated, and the small container body can be reliably secured. In addition to being able to heat, it is possible to reliably prevent the heating resistor from deteriorating, and the calorie heat means is excellent in reliability and durability.

Here, the conductive glass serving as the heating resistor of the heating means forms at least a part of the container body, but is in direct contact with the chemical solution or solution contained in the container body. Alternatively, the inner wall portion may be formed of the above-described quartz glass or synthetic resin and laminated on the outer surface. In particular, when the conductive glass serving as the heating resistor of the heating means is in direct contact with the chemical solution or solution contained in the container body, the heating efficiency is improved and the chemical resistance of the container body is improved. It can improve the storage stability of various solutions, and has excellent durability and long life.

[0024] The invention according to claim 7 is the temperature regulating container according to claim 6, wherein the conductive glass serving as the electrode of the heat absorbing portion of the Peltier element and the heat generating resistance of the heating means. It has a configuration provided with an insulating part that insulates the conductive glass to be an antibody.

With this configuration, in addition to the operation of the sixth aspect, the following operation is provided.

(1) When the Peltier element and the heating means are driven at the same time by having an insulating part that insulates the conductive glass that is the electrode of the heat absorption part of the Peltier element and the conductive glass that is the heating resistor of the heating means However, it is excellent in reliability and safety without causing trouble. Here, as a material of the insulating portion, any material can be used as long as it can insulate between the conductive glass and the conductive glass and has resistance to a chemical solution or a solution contained in the container body. In particular, the above-described quartz glass or the like is preferably used.

[0025] The invention according to claim 8 is the temperature regulating container according to any one of claims 3 to 7, wherein the conductive glass is formed on the outer surface of the container body. Has the same structure.

With this configuration, in addition to the operation of any one of claims 3 to 7, the following operation is provided.

(1) Since the conductive glass is formed on the outer surface of the container body, the film thickness can be easily controlled, and heating and cooling can be performed uniformly and without spots. Easy to maintain the temperature of the main body.

Here, as a method for forming the conductive glass on the outer surface of the container body, sputtering, spin coating, application by brush, or the like is preferably used. Similar to the above, the inner wall of the container body may be formed of quartz glass or synthetic resin, and conductive glass may be formed on the outer surface thereof.

If sputtering is applied by spin coating, conductive glass is deposited thinly and uniformly. It can be heated and cooled efficiently. In addition, when applied with a brush or the like, a thick conductive glass can be formed in a short time, which is excellent in mass productivity.

The invention's effect

[0026] As described above, according to the Peltier element of the present invention and the temperature control container including the Peltier element, the following advantageous effects can be obtained.

According to the invention described in claim 1, the following effects are obtained.

(1) By using an electrode formed of conductive glass containing vanadate as a main component, temperature control is easy and fine temperature adjustment is possible. It is possible to provide a Peltier element with excellent cooling performance, electrode reliability and durability that can reliably prevent corrosion of the electrode due to condensation and condensation.

[0027] According to the invention of claim 2, the following effects are obtained.

(1) By having a Peltier element arranged at the bottom or side of the container body, temperature adjustment is easy, and the stability and reliability of the cooling action are excellent, and the container body and the Peltier element are handled together. Therefore, it is possible to provide a temperature control container that is excellent in handling, properties, and space saving.

[0028] According to the invention described in claim 3, in addition to the effect of claim 2, the following effect is obtained.

(1) The container body made of conductive glass is excellent in thermal conductivity and chemical resistance, and versatile and reliable that can store various chemicals and solutions and efficiently heat and cool them in the temperature adjustment unit. It is possible to provide an excellent temperature control container.

(2) By processing conductive glass using a processing method such as a focused ion beam, a fine container body can be formed, which is excellent in shape flexibility and can be easily reduced in size and saved. A temperature control container excellent in space can be provided.

[0029] According to the invention described in claim 4, in addition to the effect of claim 3, the following effect is obtained.

(1) By using the conductive glass forming at least a part of the container body as the electrode of the heat absorption part of the Peltier element, the minute container body can be cooled reliably, and the container body and the Peltier element can be To provide a temperature-controlled container with excellent reliability and durability that can improve the handling and cooling efficiency as a whole, and can reliably prevent corrosion of electrodes due to chemicals and condensation. Can do.

[0030] According to the invention described in claim 5, the effect of any one of claims 2 to 4 is reduced, and the following effects are obtained.

(1) The container body can be selectively heated or cooled by Peltier elements and heating means, and the container body can be adjusted to a desired temperature in a short time. Can be provided.

[0031] According to the invention described in claim 6, in addition to the effect of claim 5, the following effect is obtained.

(1) By using conductive glass that forms at least a part of the container body as a heating resistor for the heating means, the minute container body can be heated reliably, and the container body and the heating means are integrated to facilitate handling and heating. Thus, it is possible to provide a temperature control container with excellent reliability and durability that can reliably prevent deterioration of the heating resistor.

[0032] According to the invention described in claim 7, in addition to the effect of claim 6, the following effect is obtained.

(1) When the Peltier element and the heating means are driven at the same time because the conductive glass that is the electrode of the heat absorption part of the Peltier element and the conductive glass that is the heating resistor of the heating means are insulated by the insulating part However, it is possible to provide a temperature control container that is excellent in reliability and safety without causing any trouble.

[0033] According to the invention of claim 8, the effect of any one of claims 3 to 7 is achieved, and the following effects are obtained.

(1) Easy to control the film thickness of the conductive glass film formed on the outer surface of the container body, which is excellent in mass production, can be heated and cooled uniformly and without spots, and can easily maintain the temperature of the body. It is possible to provide an excellent temperature control container.

Brief Description of Drawings

FIG. 1 is a schematic side view showing a Peltier element in embodiment 1.

[Fig. 2] (a) Plan view showing a temperature control vessel provided with a Peltier element in Embodiment 1 (b) Fig. 2 2 (a) A—A line end view

[FIG. 3] (a) Top view showing temperature control container in embodiment 2 (b) End view taken along line B-B in FIG. 3 (a)

[FIG. 4] (a) Top view showing temperature control container in Embodiment 3 (b) End view taken along line C—C in FIG. 4 (a)

[Figure 5] Differential thermal analysis results of oxide glasses of Experimental Examples 1 to 3

[Fig. 6] A plot of the electrical conductivity before and after reheating of the acid oxide glasses of Experimental Examples 1 to 3 cooled below the glass transition temperature

[Fig. 7] Diagram showing the relationship between reheating temperature, reheating time and electrical conductivity of the oxide glass in Experimental Example 2.

Explanation of symbols

[0035] 1, la Peltier element

2 electrodes

3a N-type thermoelectric semiconductor

3b P-type thermoelectric semiconductor

4a, 4b electrode

5, 16 Variable voltage application section

10, 10a, 10b Temperature control container

11, 12, 22 Container body

12a Inner wall

12b, 12c, 22b, 22c

12d, 22d insulation

15 Heating means

22a bottom

30 Temperature sensor

30a Temperature sensor fixing part

BEST MODE FOR CARRYING OUT THE INVENTION

[0036] (Embodiment 1) A Peltier device according to Embodiment 1 of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic side view showing a Peltier element according to the first embodiment.

In FIG. 1, 1 is a Peltier element according to Embodiment 1 of the present invention, 2 is an electrode of a heat absorption part of a Peltier element 1 made of a conductive glass mainly composed of vanadate, and 3a has one end part of the heat absorption part. N-type thermoelectric semiconductor of Peltier element 1 bonded to electrode 2, 3b is formed of P-type thermoelectric semiconductor of Peltier element 1 bonded to electrode 2 of the heat-absorbing part, and 4a and 4b are formed of conductive glass. The electrodes of the radiating part of the Peltier element 1 joined to the other end of the N-type thermoelectric semiconductor 3a and the P-type thermoelectric semiconductor 3b, respectively, 5 is the force from the N-type thermoelectric semiconductor 3a to the P-type thermoelectric semiconductor 3b Thus, the variable voltage application unit of the Peltier element 1 that variably controls the direct current flowing therethrough.

[0037] The conductive glass forming the heat absorbing portion electrode 2 and the heat radiating portion electrodes 4a and 4b is an oxide-based glass composition containing vanadium, norium and iron, and has a thickness of 3 mm at room temperature. The electric conductivity was 10 ^_4 to 10 _ ¹ S · cm— ¹ .

Vanadium oxide (VO) 60 to 85 mol%, barium oxide (BaO) 10 to 30 mole ^_0/0, acid

twenty five

After heating and melting a powder mixture containing 5-20 mol% of iron (Fe 2 O 3) in a platinum crucible

twenty three

Then, this was rapidly cooled to be vitrified, and the electric conductivity was adjusted by holding it for a predetermined time at a temperature of the ringing treatment at a temperature not lower than the crystallization temperature and not higher than the melting point of the glass composition.

[0038] The temperature regulating container provided with the Peltier element according to Embodiment 1 formed as described above will be described below with reference to the drawings.

FIG. 2 (a) is a plan view showing a temperature control container having a Peltier element according to Embodiment 1, and FIG. 2 (b) is an end view taken along line AA in FIG. 2 (a).

In FIG. 2, 10 is a temperature control container provided with the Peltier element 1 according to Embodiment 1 of the present invention, 11 is a temperature control container 10 made of quartz glass or the like, 10 is a container body, and 30 is at the bottom of the container body 11 A temperature sensor such as a thermocouple of a temperature control container 10 that measures the temperature of a chemical solution or solution that is fixed and stored in the container body 11, and 30a is a temperature sensor fixing part that fixes the temperature sensor 30 to the container body 11. is there.

The electrode 2 of the heat absorption part of the Peltier element 1 is attached to the side of the container body 11 by a heat conductive adhesive. Fixed to prevent a decrease in thermal conductivity.

[0039] A method of using the temperature control container including the Peltier element configured as described above will be described.

First, a chemical solution or an aqueous solution for observation or measurement is accommodated in the container body 11. The temperature of the chemical solution or solution contained in the container body 11 is measured by the temperature sensor 30 and the drive of the Peltier element 1 is controlled by the control unit (not shown) based on the measured value! By cooling, keep the chemical solution or solution at any temperature.

If the temperature measured by the temperature sensor 30 is within the allowable range of the reference set temperature force, the Peltier element 1 is not driven. If the temperature is within the allowable range, the current is controlled by the variable voltage application section 5 of the Peltier element 1, and cooling is performed so that the temperature of the container body 11 falls within the allowable range of the reference set temperature.

In the present embodiment, the arrangement and number of force Peltier elements 1 in which one Peltier element 1 is provided on the side of the container body 11 can be arbitrarily selected.

[0040] Since the Peltier element of Embodiment 1 is configured as described above, it has the following effects.

(1) By forming the electrode 2 of the endothermic part with conductive glass mainly composed of vanadate, it is possible to cool the object with a gradual temperature change. It can be held with high accuracy and has excellent cooling temperature stability.

(2) By forming the electrodes 2, 4a, 4b of Peltier element 1 with conductive glass mainly composed of vanadate, corrosion of the electrodes 2, 4a, 4b due to chemicals or condensation is surely prevented. The electrodes 2, 4a and 4b are excellent in reliability and durability.

[0041] Since the temperature control container including the Peltier element according to Embodiment 1 is configured as described above, it has the following effects.

(1) By having the Peltier element 1 disposed on the side of the container body 11, temperature adjustment is easy, cooling efficiency and reliability are excellent, and the container body 11 and the Peltier element 1 are handled as a unit. It is possible to handle and excel in handling, property and space saving.

[0042] (Embodiment 2)

Fig. 3 (a) is a plan view showing the temperature control container in Embodiment 2, and Fig. 3 (b) is a diagram of Fig. 3 (a). FIG. 6 is an end view taken along line B-B. The same components as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted.

In FIG. 3, the temperature control container 10a in the second embodiment is different from that in the first embodiment in that the container main body 12 has an insulating inner wall portion 12a formed of quartz glass or the like, and an outer wall portion 12a. A peripheral wall portion 12b, 12c formed by sputtering a conductive glass mainly composed of vanadate on the surface, and the peripheral wall portions 12b, 12c are formed of the same material as the inner wall portion 12a. And a heating means 15 disposed on the side of the container body 12 using the peripheral wall portion 12c formed of conductive glass as a heating resistor. In this point, the conductive glass forming the peripheral wall portion 12b of the container body 12 serves as an electrode of the heat absorbing portion of the Peltier element la, and the Peltier element la and the container body 12 are integrated.

Reference numeral 16 denotes a variable voltage application section of the heating means 15 that variably controls the direct current flowing through the conductive glass 12c.

[0043] A method of using the temperature control container configured as described above will be described.

First, a chemical solution or an aqueous solution for observation or measurement is stored in the container body 12. The temperature of the chemical solution or solution contained in the container body 12 is measured by the temperature sensor 30, and the control unit (not shown) drives the Peltier element 1 and the heating means 15 based on the measured value. By controlling, chemicals and solutions are adjusted and maintained at an arbitrary temperature.

If the temperature measured by the temperature sensor 30 is within the allowable range, the Peltier element la and the heating means 15 are not driven. If the temperature is within the allowable range, the current is controlled by the variable voltage application unit 5 of the Peltier element la to cool the container body 12, and if the temperature is below the allowable range, the variable voltage application unit 16 of the heating means 15 is controlled. The container body 12 is heated by controlling the current with. By repeating these operations, the temperature of the container body 12 is adjusted so that it falls within the allowable range of the reference set temperature.

It should be noted that the material of the insulating portion 12d is not limited to the present embodiment, but can be insulated between the peripheral wall portions 12b and 12c, and has resistance to chemicals and solutions stored in the container body 12. What is necessary is just to have. In this embodiment, the left and right peripheral wall portions 12b and 12c are divided and insulated by the insulating portion 12d. However, the number of divisions and the dividing position of the peripheral wall portion are arbitrarily selected. can do. For example, the peripheral wall portion can be divided into upper and lower parts, and the Peltier element la and the heating means 15 can be provided respectively.

In the present embodiment, the force Peltier element la and the heating means 15 are each provided on the opposing surface of the container body 12 one by one. The arrangement and number of the Peltier elements la and the heating means 15 can be arbitrarily selected. .

The temperature sensor fixing part 30a may be formed integrally with the insulating part 12d, or may be formed of a separate member having insulating properties.

Since the temperature control container including the Peltier element according to the second embodiment is configured as described above, in addition to the actions obtained in the first embodiment, the following actions are provided.

(1) By forming the peripheral wall parts 12b and 12c of the container body 12 with conductive glass, it is possible to improve the thermal conductivity, and various chemicals and solutions can be stored and heated and cooled efficiently in the temperature adjustment part. It can be used and has excellent versatility and reliability.

(2) Electrode force of the heat absorption part of the Peltier element la The peripheral wall part 12b of the container body 12 made of conductive glass allows the container body 12 and the Peltier element la to be easily integrated into a single piece. The container body 12 can be reliably cooled, and corrosion of the electrode due to chemicals and condensation can be reliably prevented, and the reliability and durability of the Peltier element la are excellent.

(3) Since the heating means 15 disposed on the side of the container main body 12 is provided, the container main body 12 can be easily and reliably heated, and the heating efficiency and reliability are excellent.

(4) Since the heating resistor of the heating means 15 is the peripheral wall portion 12c of the container main body 12 made of conductive glass, the container main body 12 and the heating means 15 can be easily integrated, The container body 12 can be reliably heated and the heating resistor can be reliably prevented from deteriorating, and the heating means 15 is excellent in reliability and durability.

(5) Since the container main body 12 has both the Peltier element la and the heating means 15, the container main body 12 can be adjusted to a desired temperature in a short time and is excellent in versatility and handling.

(6) It has an insulating portion 12d that insulates the conductive glass peripheral wall portion 12b that serves as an electrode of the heat absorption portion of the Peltier element la and the conductive glass peripheral wall portion 12c that serves as a heating resistor of the heating means 15. As a result, even when the Peltier element la and the heating means 15 are driven at the same time, it is excellent in reliability and safety without causing trouble. (7) Since the main component of the conductive glass forming the peripheral wall portions 12b and 12c is vanadate, the electrical conductivity is increased to improve the cooling efficiency by the Peltier element la and the heating efficiency by the heating means 15. It is excellent in energy saving.

(8) Since the peripheral walls 12b and 12c made of conductive glass are formed on the outer surface of the inner wall 12a of the container body 12, the thickness of the peripheral walls 12b and 12c can be easily controlled. Heating and cooling can be performed uniformly and without spots, and the stability of the temperature maintenance of the main body 12 is excellent.

[Embodiment 3]

FIG. 4 (a) is a plan view showing the temperature control container in Embodiment 3, and FIG. 4 (b) is an end view taken along the line CC of FIG. 4 (a). The same components as those in the second embodiment are denoted by the same reference numerals and description thereof is omitted.

In FIG. 4, the temperature control container 10b in the third embodiment is different from the second embodiment in that the container main body 22 has an insulating bottom 22a formed of quartz glass or the like, and the same as in the second embodiment. The peripheral wall portions 22b and 22c are made of conductive glass, and the peripheral wall portions 22b and 22c are divided into left and right by an insulating portion 22d formed of the same material as that of the bottom portion 22a.

Since the method of using the temperature control container in the third embodiment is the same as that in the second embodiment, the description thereof is omitted.

[0047] Since the temperature control container of the third embodiment is configured as described above, in addition to the actions obtained in the third embodiment, the following actions are provided.

(1) By forming the peripheral wall portions 22b and 22c of the container body 22 with conductive glass, fine processing can be performed using a processing method such as a focused ion beam, and the container body has excellent flexibility and shape. 22 is easy to downsize and has excellent space saving.

(2) Since the main component of the conductive glass is vanadate, it is easy to mold complex shapes and has excellent processability, and can form various types of container body 22 as well as being smaller and lighter. Easy to use, resource-saving and mass-productive.

Example

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is based on these examples. It is not limited.

(Experiment 1)

Barium oxide (BaO) is 10 mole ^_0/0, vanadium pentoxide (VO) force 0 mole ^_0/0, triacid

twenty five

Weigh each reagent grade reagent so that the total amount is 10 g with 10 mol% ferric oxide (Fe 2 O 3),

twenty three

After mixing in an agate mortar, the mixture was placed in a platinum crucible, and the mixture in the platinum crucible was melted by heating in the air for 90 minutes in an electric furnace heated to 1000 ° C. The melt was poured onto a stainless steel plate having a thickness of 10 mm and quenched to below the glass transition temperature, whereby the oxide glass of Experimental Example 1 was obtained.

(Experiment 2)

Barium oxide (BaO) is 20 mole ^_0/0, vanadium pentoxide (VO) force 70 mole ^_0/0, triacid

twenty five

Weigh each reagent grade reagent so that the total amount of diiron ferrous (Fe 2 O 3) is 10 mol% and 10 g.

twenty three

Except that, the acid oxide glass of Experimental Example 2 was obtained in the same manner as Experimental Example 1.

(Experiment 3)

Barium oxide (BaO) is 30 mole ^_0/0, vanadium pentoxide (VO) force 0 mole ^_0/0, triacid

twenty five

twenty three

Except that, the acid oxide glass of Experimental Example 3 was obtained in the same manner as Experimental Example 1.

[0049] (Results of differential thermal analysis of acid-containing glass of Experimental Examples 1 to 3)

Differential thermal analysis (DTA) of the oxide glasses of Experimental Examples 1 to 3 was performed. The differential thermal analysis (DTA) conditions are as follows: ex alumina is used as the reference material, and the temperature rise rate is 10 ° CZ in a nitrogen atmosphere.

FIG. 5 shows the results of differential thermal analysis of the oxide glasses of Experimental Examples 1 to 3.

From Fig. 5, as the molar ratio of barium oxide increases and the molar ratio of divanadium pentoxide decreases, the glass transition temperature (Tg) and the crystallization temperature (Tc) rise. It was 362 ° C, in Experiment 2 it was 392 ° C, and in Experiment 3 it was 433 ° C. The sharp endothermic peak seen in the temperature range above the crystallization temperature (Tc) shows the melting point, which is 600 ° C or higher in Experimental Example 1, 540 ° C in Experimental Example 2, and 540 ° C in Experimental Example 3. It was 563 ° C.

[0050] (Relationship between reheating temperature and electrical conductivity)

Experimental example cooled to below the glass transition temperature Reheating was performed at 0 ° C, 500 ° C, and 550 ° C for 1 hour, and the electric conductivity at 25 ° C of the oxide glass before and after the reheating was measured by a DC four-terminal method.

Figure 6 is a plot of the electrical conductivity before and after reheating of the acid glass of Experimental Examples 1 to 3 cooled below the glass transition temperature. In Fig. 6, the horizontal axis represents the reheating temperature (° C), and the vertical axis represents the electrical conductivity σ (S, cm– ¹ ) at 25 ° C.

From Fig. 6, when the oxide glass of Experimental Example 1 is reheated for 1 hour at 500 to 550 ° C, which is the temperature above the crystallization temperature (362 ° C) and below the melting point (600 ° C or higher). The electrical conductivity at 25 ° C was increased by about 4 orders of magnitude compared to before reheating.

In Fig. 6, the electrical conductivity when reheated at 400 ° C for 1 hour was the same as before reheating, but by reheating at 400 ° C for 2 hours, it was at room temperature (25 ° C). The electrical conductivity could be about 10 ^_3 S'cm ^_1 . In the oxide glass of Experimental Example 1, the holding time when the reheating temperature is 400 ° C is considered to be short in 1 hour.

Also, from Fig. 6, when the oxide glass of Experimental Example 2 is reheated for 1 hour at 400 to 500 ° C, which is higher than the crystallization temperature (392 ° C) and lower than the melting point (540 ° C). The electrical conductivity at 25 ° C was higher than 10 ^_3 S 'cm— ¹ . In particular, when reheated at 500 ° C, a high electrical conductivity of 10 ^_1 S 'cm- ¹ or higher was achieved. When reheated at 550 ° C, which is higher than the melting point (540 ° C) for 1 hour, part of it crystallized.

In addition, from FIG. 6, when the oxide glass of Experimental Example 3 is reheated at 500 ° C, which is higher than the crystallization temperature (433 ° C) and below the melting point (563 ° C), 25 ° C The electrical conductivity of the material was higher than 10 ^_2 S • cm— ¹ .

When reheated at 550 ° C, which is close to the melting point (563 ° C) for 1 hour, part of it crystallized, so the electrical conductivity of the oxide glass reheated at 550 ° C is plotted! / ,! This is probably because the molar ratio of barium oxide to nivanadium pentoxide was increased. By shortening the holding time and reheating at 550 ° C for 0.5 hours, the electrical conductivity at 25 ° C was reduced to about 10 ^_2 S · cm– ¹ without crystallization.

Based on the above, the electrical conductivity at room temperature (25 ° C) has been greatly improved through a reheating process in which the oxide glass (conductive glass) is kept in the temperature range above the crystallization temperature and below the melting point. It became clear that it can be enhanced. In addition, it was found that the electrical conductivity improves as the reheating temperature increases in the temperature range where crystal precipitation and melting do not occur remarkably. In addition, the retention time can be shortened as the reheating temperature increases. From these phenomena, it is considered that the mechanism by which the electric conductivity is improved by reheating above the crystallization temperature and below the melting point is due to the activity energy of the electrons.

[0051] In addition to these experimental examples, vanadium oxide (V 2 O), barium oxide (BaO), acid

twenty five

The molar ratio of iron oxide (Fe 2 O 3) is 40 to 98 mol%, 1 to 40 mol%, and 1 to 20 mol%, respectively.

twenty three

Various oxide glasses were prepared so as to be in the range, the crystallization temperature and melting point of each were determined, and the electrical conductivity at room temperature before and after the reheating process was measured. Reheating as in these experimental examples was performed. It was confirmed that the electrical conductivity increased through the process.

A mixture of vanadium oxide (V O), barium oxide (BaO) and iron oxide (Fe O)

2 5 2 3

Vanadium oxide (V o), dipentaoxide, which can be obtained only by using an oxide glass produced by melting and cooling.

twenty five

An acidic glass produced by melting and cooling a mixture of phosphorus (P 2 O 3) and barium oxide (BaO),

twenty five

Melting and cooling a mixture of vanadium oxide (V O), potassium oxide (K O), and iron oxide (Fe O)

2 5 2 2 3

It was also confirmed that the electrical conductivity of the oxide glass produced in this way increased through the reheating process.

[0052] (Relationship between reheating time and electrical conductivity)

(Example 1)

Re-heated the oxide glass of Experimental Example 2 cooled to below the glass transition temperature in the atmosphere at 500 ° C, which is a temperature exceeding the crystallization temperature (392 ° C) and below the melting point (540 ° C), The electrical conductivity at 25 ° C was measured after taking out from the furnace at regular intervals.

(Example 2)

Re-heated the oxide glass of Example 2 cooled to below the glass transition temperature in the atmosphere at 400 ° C, which is a temperature exceeding the crystallization temperature (392 ° C) and below the melting point (540 ° C), The electrical conductivity at 25 ° C was measured after taking out from the furnace at regular intervals.

(Example 3)

The oxide glass of Experiment 2 cooled to below the glass transition temperature was reheated in the atmosphere at 350 ° C, which is the glass transition temperature (328 ° C) or higher and the crystallization temperature (392 ° C) or lower. From inside the furnace The sample was taken out at regular intervals and the electrical conductivity at 25 ° C was measured.

FIG. 7 is a graph showing the relationship between the reheating temperature and reheating time of the oxide glass of Experimental Example 2 and electrical conductivity. In FIG. 3, the horizontal axis represents the holding time at the reheating temperature, and the vertical axis represents the electrical conductivity σ (S.cm- ¹ ) at 25 ° C.

In Examples 1 and 2, the acid-containing glass of Experimental Example 2 cooled to below the glass transition temperature was reheated in the atmosphere at a temperature exceeding the crystallization temperature (392 ° C) and below the melting point (540 ° C). It was confirmed that the electrical conductivity could be improved by more than three orders of magnitude by reheating for only 30 minutes, and that the electrical conductivity hardly fluctuated even if reheating was continued. In addition, it was confirmed that Example 1 having a higher reheating temperature than Example 2 can increase the electrical conductivity.

On the other hand, in Example 3, which was reheated at a temperature not lower than the glass transition temperature (328 ° C) and not higher than the crystallization temperature (392 ° C), the electrical conductivity increased as the holding time at the reheating temperature increased. It was confirmed that the electrical conductivity could not be kept constant unless maintained for 180 minutes or longer. In addition, it was confirmed that the electrical conductivity of Example 3 was lower by one digit or more than that of Examples 1 and 2.

From the above, according to the present embodiment, the electrical conductivity does not vary by keeping the time for maintaining the reheating temperature appropriately according to the reheating temperature. The electrical conductivity can be drastically increased even if it is held in the temperature range for about 30 minutes, and even if the holding time varies, the electrical conductivity does not vary and the production stability is remarkably excellent and preferable. It was revealed. Further, by changing the heating time and the like in the reheating step, it was found that the magnitude of the electrical conductivity of the vanadate glass at room temperature can be precisely designed controlled 10 ^_4 S'cm ^_1 or more regions. When the conductive glass obtained in this way is used as an electrode of a Peltier element, the temperature change can be performed slowly and finely, and the temperature of the object can be accurately maintained within a substantially constant range. It was able to be done and was excellent in stability of cooling performance.

Industrial applicability

[0054] The present invention provides a Peltier device that can maintain a constant temperature with high accuracy by using a conductive glass mainly composed of vanadate as an electrode, is easy to adjust the temperature, and has excellent handleability. In addition, the container body is easy to process, has excellent shape flexibility, and has a fine space It can be formed to contain chemicals and aqueous solutions, and has excellent chemical resistance and storage stability. In addition, a fine space containing chemicals and aqueous solutions can be efficiently heated and cooled to maintain any temperature. Providing temperature control containers equipped with Peltier elements with excellent reliability, versatility, and workability that enable efficient observation and various measurements in a short time. This improves the handling of chemicals and aqueous solutions.

Claims

The scope of the claims

[1] A Peltier element having a heat absorption part and a heat generation part, wherein at least the electrode of the heat absorption part is formed of a conductive glass containing vanadate as a main component.

[2] A temperature control container comprising: a container main body; and the Peltier element according to claim 1 disposed on a bottom portion or a side portion of the container main body.

[3] The temperature regulating container according to [2], wherein at least a part of the container body is formed of the conductive glass.

4. The temperature control container according to claim 3, wherein the electrode of the heat absorption part of the Peltier element is the conductive glass that forms at least a part of the container body.

[5] The temperature control container according to any one of claims 2 to 4, further comprising heating means disposed on a bottom portion or a side portion of the container main body.

6. The temperature control container according to claim 5, wherein the heating resistor of the heating means is the conductive glass forming at least a part of the container body.

[7] The present invention further includes an insulating portion that insulates the conductive glass serving as the electrode of the heat absorbing portion of the Peltier element and the conductive glass serving as the heating resistor of the heating means. 6. The temperature control container according to 6.

8. The temperature regulating container according to any one of claims 3 to 7, wherein the conductive glass is formed by being formed on an outer surface of the container body.