WO2015041315A1 - 熱電対及びその製造方法 - Google Patents
熱電対及びその製造方法 Download PDFInfo
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- WO2015041315A1 WO2015041315A1 PCT/JP2014/074826 JP2014074826W WO2015041315A1 WO 2015041315 A1 WO2015041315 A1 WO 2015041315A1 JP 2014074826 W JP2014074826 W JP 2014074826W WO 2015041315 A1 WO2015041315 A1 WO 2015041315A1
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- thermocouple
- oxide
- protective tube
- tube
- wire
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K1/00—Details of thermometers not specially adapted for particular types of thermometer
- G01K1/08—Protective devices, e.g. casings
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K1/00—Details of thermometers not specially adapted for particular types of thermometer
- G01K1/08—Protective devices, e.g. casings
- G01K1/12—Protective devices, e.g. casings for preventing damage due to heat overloading
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
- G01K7/04—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples the object to be measured not forming one of the thermoelectric materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
Definitions
- the present invention relates to a thermocouple and a manufacturing method thereof.
- oxide single crystals such as power semiconductors, glass, other laser elements, voltage elements, or scintillator elements are each required to have improved performance, and their manufacturing temperature tends to increase.
- the engine combustion temperature in the aerospace field is required to improve performance, and the temperature is getting higher and higher.
- a radiation thermometer is generally used for temperature measurement.
- the energy of infrared rays and visible rays corresponding to the temperature of an object is measured and converted into temperature.
- the surrounding environment especially when there is water vapor, dust or gas
- the space itself cannot measure the temperature in principle. Therefore, there is a problem that detailed temperature measurement cannot be performed.
- Thermocouple is a highly accurate and stable temperature sensor using the Seebeck effect.
- a high temperature field of 1500 ° C. or higher it cannot be stably used in a harsh environment such as an oxidizing atmosphere or a carbon reducing atmosphere, and relies on a calculated value by combustion gas analysis or a temperature simulation from a heating output.
- thermocouples cannot be used stably in an oxidizing atmosphere or a carbon reducing atmosphere is due to the relationship between the wire, the protective tube, and the insulator between them.
- the thermocouple used at high temperature is, for example, a thermocouple using Pt or Rh as a strand, a thermocouple using Ir or Rh as a strand, or a thermocouple using W or Re as a strand.
- Thermocouples using Pt and Rh as strands are vulnerable to a carbon reducing atmosphere.
- a thermocouple using W or Re as a strand cannot be used due to oxidation damage in an oxidizing atmosphere.
- thermocouple using Ir and Rh as a strand is more durable than other thermocouples in both environments, but it cannot be said that the durability is sufficient. Therefore, a protective tube is used.
- a thermocouple is disclosed in which a metal wire consisting of one pair is inserted into an insulating tube, the insulating tube is inserted into a protective tube, and a gap is filled between the protective tube and the raw wire.
- a thermocouple in which a strand coated with colloidal silica is inserted into an alumina protective tube or a quartz protective tube is disclosed (for example, see Patent Document 2).
- thermocouple technology as a method for suppressing volatilization loss of platinum group noble metals constituting a high temperature apparatus, a method of forming a coating layer having a thickness of 50 to 500 ⁇ m made of stabilized zirconia on the outer surface of the high temperature apparatus by thermal spraying Is disclosed (for example, see Patent Document 3).
- thermocouple A method for manufacturing a sheathed thermocouple is disclosed (for example, see Patent Document 4).
- JP 2002-350240 A Japanese Patent Laid-Open No. 10-19688 JP 2012-132071 A JP 2010-060445 A
- Patent Document 1 describes using alumina as an insulating tube
- Patent Document 2 describes using alumina as a protective tube.
- alumina since the strength of alumina deteriorates at 1900 ° C. or higher, these thermocouples cannot be used at 1900 ° C. or higher.
- Patent Document 2 describes that a strand is coated with colloidal silica and that quartz is used as a protective tube.
- silicon oxide softens at 1700 ° C. or higher, and at higher temperatures, part of it is thermally decomposed and volatilizes. When the decomposed and volatilized components adhere to the strands, the strands have a low melting point, and there is a problem of melting or embrittlement and breaking.
- thermocouple used at a high temperature
- thorium oxide or beryllium oxide is used in addition to aluminum oxide.
- thorium oxide is a radioactive substance, and beryllium oxide is toxic, so its use is limited.
- An object of the present invention is to provide a thermocouple capable of performing direct temperature measurement stably in a high temperature environment (1500 ° C. to 2300 ° C.) and a method for manufacturing the same.
- thermocouple is a thermocouple having at least a protective tube and a strand, wherein the protective tube and the strand are insulated by an insulator, and the insulator is a powder or a molded body.
- the insulator is a powder or a molded body.
- One or both of them are characterized by being made of at least one of zirconium oxide, hafnium oxide, or a composite oxide of zirconium and hafnium.
- the insulator preferably has a content of each element of Al, Fe, Si and Ti of 100 mass ppm or less and a content of C of 10 mass ppm or less. . When used at a high temperature of 1900 ° C. or higher, durability can be further enhanced.
- the surface of the wire is preferably covered with an oxygen barrier film, and the thickness of the oxygen barrier film is preferably 20 nm or more and 800 nm or less.
- the oxidation volatilization or oxidative deterioration of the strands can be suppressed. Further, it is possible to prevent the wire from having a low melting point due to adhesion of impurities decomposed and volatilized from the insulator.
- the strand is made of one or two elements selected from Ir, Pt, Rh, Mo, Re, Nb, Ta, and W.
- the material can be selected according to the temperature to be measured.
- the oxygen barrier film covering the surface of the element wire includes an oxide as a main component, and the element bonded to oxygen of the oxide is either one or both of Hf and Zr. Preferably there is. Lowering of the melting point of the oxide can be prevented.
- thermocouple In the thermocouple according to the present invention, at least one of the entire outer surface of the protective tube or a part thereof, or the entire inner surface of the protective tube or a part thereof, is covered with an oxygen barrier film,
- the thickness of the oxygen barrier film is preferably 20 nm or more and 800 nm or less. Oxidative volatilization or oxidative degradation of the protective tube can be suppressed.
- the protective tube can be prevented from having a low melting point due to the adhesion of impurities decomposed and volatilized from the insulator.
- the protective tube is preferably formed using one or two elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W.
- the material can be selected according to the atmosphere for temperature measurement.
- the oxygen barrier film covering the outer surface or the inner surface of the protective tube contains an oxide as a main component, and the element bonded to oxygen of the oxide is either Hf or Zr. Or both are preferred. Lowering of the melting point of the oxide can be prevented.
- thermocouple The method of manufacturing a thermocouple according to the present invention is characterized in that no wire drawing is performed after the strand and the insulator are inserted into the protective tube.
- the present invention can provide a thermocouple capable of performing direct temperature measurement stably in a high temperature environment (1500 ° C. or higher and 2300 ° C. or lower) and a method for manufacturing the same.
- thermocouple which concerns on 1st embodiment
- (a) is an example of the partial expanded sectional view of a strand
- (b) is the partial expanded cross section of a protection tube
- 3 is a SEM image near a broken line according to Comparative Example 1.
- EDX energy dispersive characteristic X-ray-spectroscopy
- FIG. 1 is an enlarged side sectional view showing a part of the thermocouple according to the first embodiment, (a) is an example of a partially enlarged sectional view of a strand, and (b) is a protective tube. It is an example of a partial expanded sectional view of.
- the thermocouple 10 according to the first embodiment is a thermocouple having at least a protective tube 16 and strands 12 and 13, and the protective tube 16 and the strands 12 and 13 are insulated by an insulator 15.
- the insulator 15 is a powder and is made of at least one of zirconium oxide, hafnium oxide, or a composite oxide of zirconium and hafnium.
- the strands 12 and 13 are preferably made of one or two elements selected from Ir, Pt, Rh, Mo, Re, Nb, Ta and W.
- the material can be selected according to the temperature to be measured.
- the form formed using one of the elements selected from Ir, Pt, Rh, Mo, Re, Nb, Ta, and W may be a dispersion strengthened alloy in addition to a pure metal.
- the dispersion strengthened alloy is, for example, an oxide dispersion strengthened (ODS, Oxide Dispersion Strengthened) alloy (for example, ODS platinum).
- ODS Oxide Dispersion Strengthened
- alloys composed of two or more elements selected from Ir, Pt, Rh, Mo, Re, Nb, Ta and W include Pt—Rh, Ir—Rh, Mo—Re, Mo—Nb, Mo. -Ta, W-Re, W-Mo or Nb-Ta.
- it may be a dispersion strengthened alloy in which an oxide or the like is dispersed in each alloy.
- the strands 12 and 13 include, for example, a combination of Pt-Rh and Pt-Rh having different components, a combination of Pt-Rh and Pt, a combination of Pt-Ir and Pt, a combination of Rh and Pt, and Rh Combination of Pt-Rh, combination of Pt-Mo and Pt, combination of Ir-Rh and Ir, combination of Ir-Rh and Ir-Rh having different components, combination of Ir and Pt-Rh, Different W-Re and W-Re combinations, W and W-Re combinations, Mo and Re combinations, Mo and Nb combinations, Mo and Ir combinations, Mo and W combinations, W And Ir or W and Ta. These combinations are merely examples, and the combinations of the strands 12 and 13 are not particularly limited in the present invention.
- the surfaces of the strands 12 and 13 are preferably covered with an oxygen barrier film 17a as shown in FIG. Further, the thickness of the oxygen barrier film 17a is preferably 20 nm or more and 800 nm or less. The thickness of the oxygen barrier film 17a is more preferably 40 nm or more and 600 nm or less, and particularly preferably 50 nm or more and 80 nm or less. If the thickness of the oxygen barrier film 17a is less than 20 nm, the oxidization volatilization or oxidative degradation of the strands 12 and 13 and the lower melting point of the strands 12 and 13 due to the adhesion of impurities decomposed and volatilized from the insulator 15 can be suppressed. There are cases where it is not possible.
- the oxygen barrier film 17a may be peeled off or cracked due to a difference in thermal expansion coefficient from the material of the strands 12 and 13. As a result, it may be impossible to suppress the oxidation volatilization or deterioration of the strands 12 and 13 and to suppress the lower melting point of the strands 12 and 13 due to the adhesion of impurities decomposed and volatilized from the insulator 15.
- the oxygen barrier film 17a may cover the entire surface of the strands 12 and 13, or may cover a part thereof.
- the form in which the oxidation barrier film covers a part of the strands 12 and 13 is, for example, a form that covers only a part where oxidation deterioration or oxidation volatilization is a concern.
- the oxygen barrier film 17a covering the surfaces of the strands 12 and 13 contains an oxide as a main component, and the element bonded to oxygen in the oxide is either one or both of Hf and Zr.
- the material of the oxygen barrier film 17 a that covers the surfaces of the strands 12 and 13 is more preferably the same as the material of the insulator 15. Lowering of the melting point of the oxide can be prevented.
- the oxygen barrier film 17a is a film containing hafnium oxide or a film containing zirconium oxide.
- the oxygen barrier film 17a is a film containing hafnium oxide and zirconium oxide, or a film containing a complex oxide of zirconium and hafnium.
- the ratio of hafnium and zirconium is not particularly limited.
- the ends of the wires 12 and 13 opposite to the temperature measuring contact 14 may be connected to compensating wires (not shown), respectively.
- the end portion on the opposite side to the connection portion (compensation contact) with the wires 12 and 13 is connected to a terminal (not shown) of the thermoelectromotive force measuring device.
- the temperature measuring contact 14 and a terminal (not shown) are electrically connected via a compensating lead (not shown).
- the material of the compensating lead wire (not shown) is not particularly limited.
- the surface of the compensating conductor may be covered with an insulating layer (not shown) containing glass fiber, polytetrafluoroethylene, vinyl chloride, silicon, or the like.
- the protective tube 16 is preferably formed using one or two elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W.
- the material can be selected according to the atmosphere for temperature measurement.
- the form formed using one of elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta, and W may be a dispersion strengthened alloy in addition to a pure metal.
- the dispersion strengthened alloy is, for example, an oxide dispersion strengthened (ODS, Oxide Dispersion Strengthened) alloy (for example, ODS platinum).
- the protective tube 16 is a hollow member having an open end, and the open end is sealed with a sealing portion 16a after the strands 12, 13 and the insulator 15 are accommodated in the protective tube 16. Alternatively, the opened one end may be sealed with the sealing portion 16a after gas substitution or decompression after accommodating the strands 12, 13 and the insulator 15 in the protective tube 16.
- the thickness of the protective tube 16 is preferably 0.1 to 5.0 mm, and more preferably 0.5 to 2.0 mm. By reducing the thickness of the protective tube, heat can be transferred easily, and the speed response can be improved.
- the shape of the protective tube 16 is not particularly limited.
- the thickness of the oxygen barrier film 17b is preferably 20 nm or more and 800 nm or less.
- the thickness of the oxygen barrier film 17b is more preferably 40 nm or more and 600 nm or less, and particularly preferably 50 nm or more and 80 nm or less.
- the thickness of the oxygen barrier film 17b is less than 20 nm, it may not be possible to suppress the oxidative volatilization or oxidative degradation of the protective tube 16 and to suppress the lowering of the melting point of the protective tube 16 due to adhesion of impurities decomposed and volatilized from the insulator 15. . If the thickness of the oxygen barrier film 17b exceeds 800 nm, the oxygen barrier film 17b may be peeled off or cracked due to the difference in thermal expansion coefficient from the material of the protective tube 16.
- the form in which the oxygen barrier film 17b covers the protective tube 16 includes, for example, a form that covers the entire outer surface of the protective tube 16, a form that covers a part of the outer surface of the protective tube 16, and the entire inner surface of the protective tube 16 A form covering a part of the inner surface of the protective tube 16, a form covering the entire outer surface and the entire inner surface of the protective tube 16, an entire outer surface of the protective tube 16 and a part of the inner surface A form of covering, a form of covering a part of the outer surface of the protective tube 16 and the entire inner surface, or a form of covering a part of the outer surface of the protective tube 16 and a part of the inner surface.
- the form in which the oxidation barrier film covers a part of the outer surface and / or the inner surface of the protective tube 16 is, for example, a form that covers only a part where oxidation deterioration and oxidation volatilization are concerned.
- the oxygen barrier film 17b that covers the outer surface or the inner surface of the protective tube 16 contains an oxide as a main component, and the element that binds to oxygen in the oxide is preferably one of or both of Hf and Zr. .
- the material of the oxygen barrier film 17b that covers the surface of the protective tube 16 is more preferably the same as the material of the insulator 15. Lowering of the melting point of the oxide can be prevented.
- the oxygen barrier film 17b is a film containing hafnium oxide or a film containing zirconium oxide.
- the oxygen barrier film 17b is a film containing hafnium oxide and zirconium oxide, or a film containing a complex oxide of zirconium and hafnium.
- the ratio of hafnium and zirconium is not particularly limited.
- the protective tube 16 and the wires 12 and 13 are insulated by an insulator 15.
- insulated means, for example, that a resistance value at 2000 ° C. in an Ar atmosphere is 10 ⁇ ⁇ cm or more.
- the insulator 15 is one of zirconium oxide powder, hafnium oxide powder, or a mixed powder of zirconium oxide powder and hafnium oxide powder, and is filled between the protective tube 16 and the strands 12 and 13.
- the mixing ratio of the mixed powder of zirconium oxide powder and hafnium oxide powder is not particularly limited. In the present invention, the shape and average particle diameter of the powder are not particularly limited.
- the zirconium oxide includes a form that is stabilized zirconia.
- hafnium oxide includes a form that is stabilized hafnia.
- stabilized zirconia or stabilized hafnia that can be suitably used is limited to the specific types shown below.
- Hafnium oxide has a melting point of 2758 ° C., but undergoes phase transformation at 1700 ° C.
- Zirconium oxide has a melting point of 2715 ° C., but undergoes phase transformation at 1170 ° C. In any case, there is a volume change of 4 to 5% upon phase transformation.
- an oxide such as aluminum oxide, titanium oxide, or silicon oxide is added to suppress the occurrence of phase transformation and improve the moldability.
- an oxide such as aluminum oxide, titanium oxide, or silicon oxide is added to suppress the occurrence of phase transformation and improve the moldability.
- some of these oxides may be thermally decomposed and adhere to the strands or protective tubes to lower the melting point.
- the stabilized zirconia that can be suitably used in the present embodiment is, for example, yttria stabilized zirconia, calcia stabilized zirconia, or magnesia stabilized zirconia.
- stabilized hafnia is used as hafnium oxide, it is preferable not to use alumina-stabilized hafnia, titania-stabilized hafnia and silica-stabilized hafnia.
- the stabilized hafnia that can be suitably used in the present embodiment is, for example, yttria stabilized hafnia, calcia stabilized hafnia or magnesia stabilized hafnia.
- the insulator 15 is powder, even if the insulator 15 is made of zirconium oxide or hafnium oxide not containing a stabilizer, the insulator 15 is a phase transformation of zirconium oxide or hafnium oxide. There is no worry of breakage due to volume change due to.
- the content of each element of Al, Fe, Si, and Ti is 100 mass ppm or less and the content of C is 10 mass ppm or less.
- the content of each element of Al, Fe, Si and Ti is more preferably 80 ppm by mass or less, and particularly preferably 40 ppm by mass or less.
- the content of each element of Al, Fe, Si, Ti, and C is set within a predetermined range, thereby preventing the wires 12 and 13 and the protective tube 16 from being damaged due to the low melting point. Can do.
- the insulator 15 preferably has a total content of Al, Fe, Si, Ti and C of 200 mass ppm or less, and more preferably 140 ppm or less.
- FIG. 2 is an enlarged side sectional view showing a part of the thermocouple according to the second embodiment.
- the thermocouple 1 according to the second embodiment has the same basic configuration as the thermocouple 10 according to the first embodiment except that the insulator 5 is a molded body.
- description of common points is omitted, and different points will be described.
- the molded body is, for example, a hollow member opened at both ends.
- two elongated holes 5a and 5b are provided in one tube, and the strands 12 and 13 are passed through the elongated holes 5a and 5b, respectively.
- the insulating tube for the strand 12 and the strand 13 are shown.
- the insulating tube may be a hollow member in which each insulating tube is provided with one elongated hole.
- the temperature measuring contact 14 may be brought into contact with the inner wall surface of the protective tube 16 or may be non-contact.
- FIG. 2 shows a form in which the compensation contact (not shown) is arranged outside the protective tube 16, the compensation contact (not shown) may be arranged inside the protective tube 16.
- the insulator 5 is a molded body and is made of zirconium oxide or hafnium oxide not containing a stabilizer
- the volume of the insulator 5 due to phase transformation of zirconium oxide or hafnium oxide can be reduced by not forming the molded body densely. It is possible to prevent breakage due to change.
- gaps such as pores are generated between the constituent particles of the molded body, and this gap absorbs strain due to volume change, so that breakage can be prevented.
- a molding method that does not make a compact compactly includes, for example, adding a large amount of binder to the raw material powder, forming a calcined body with many loopholes of the binder-derived gas generated during calcining, and then calcining.
- the relative bulk density of the molded body (molded body after sintering) as the insulator 5 is preferably 95% or less, and more preferably 90% or less.
- the relative bulk density is a ratio (percentage) of the bulk density to the theoretical density.
- thermocouple (not shown) according to the third embodiment is basically the same as the thermocouple 10 according to the first embodiment and the thermocouple 1 according to the second embodiment, except that the insulator is both a powder and a molded body.
- the same configuration is the same.
- thermocouples 1 and 10 Next, a method for manufacturing the thermocouples 1 and 10 according to this embodiment will be described.
- Oxygen barrier films 17a and 17b are formed on the surfaces of the strands 12 and 13 and the protective tube 16 as necessary.
- the formation method of the oxygen barrier films 17a and 17b is not particularly limited. For example, a thermal spraying method, a CVD (Chemical Vapor Deposition) method, a PVD (Physical Vapor Deposition) method, a coating pyrolysis method, a spray pyrolysis method, or a spray pyrolysis method. Is the law.
- the manufacturing method of the thermocouple 10 according to the first embodiment includes, for example, a step of welding one end of the strands 12 and 13 to form the temperature measuring contact 14, and the strands 12 and 13 to the protective tube 16. There are a step of inserting, a step of filling the insulator 15 between the protective tube 16 and the wires 12 and 13, and a step of sealing the protective tube 16 with the sealing portion 16a. Moreover, before the process of sealing the protective tube 16, you may have the process of carrying out gas substitution or pressure reduction of the inside of the protective tube 16. FIG. The present invention is not limited to this procedure.
- the manufacturing method of the thermocouple 1 according to the second embodiment includes, for example, a process of passing the wires 12 and 13 through the elongated holes 5a and 5b of the insulator 5 and welding one end of the wires 12 and 13. It includes a step of forming the temperature measuring contact 14, a step of inserting the wires 12, 13 and the insulator 5 into the protective tube 16, and a step of sealing the insulator 5 and the protective tube 16 with the sealing portion 16a. Moreover, before the process of sealing the protective tube 16, you may have the process of carrying out gas substitution or pressure reduction of the inside of the protective tube 16. FIG. The present invention is not limited to this procedure.
- thermocouples 1 and 10 In the manufacturing method of the thermocouples 1 and 10 according to the present embodiment, after the strands 12 and 13 and the insulators 5 and 15 are inserted into the protective tube 16, no wire drawing is performed.
- a so-called sheath thermocouple is generally drawn until a predetermined outer diameter is obtained in a state where an element wire and an insulator are inserted into a metal tube as described in paragraph 0022 of Patent Document 4, for example.
- Manufactured by processing reducing diameter
- the wire drawing (reducing diameter) is, for example, cold drawing by rotary swaging or hole dies. At this time, when the insulator is a molded body, the molded body is crushed into powder.
- wire drawing is performed, the powder becomes dense and the strands are constrained, so that not only is the wire easily broken during processing but also the expansion and contraction of the strands caused by the temperature rise and fall are hindered, so the wire breaks easily.
- wire drawing is not performed, so that it is difficult to break.
- thermocouple of the present invention In a high temperature atmosphere of 1500 ° C. or higher, the reaction of constituent members such as protective tubes, insulators, and strands or the influence of impurities appears remarkably. As a result, alloying and a lower melting point occur due to an unexpected reaction, and an electromotive force abnormality or a lifetime reduction of the thermocouple occurs. For this reason, it is a very harsh atmosphere when measuring temperature using a thermocouple. In the case of a thermocouple using platinum, even in an air atmosphere, if it is used in a harsh environment near the upper limit temperature (for example, 1500 ° C or higher), the life will be shortened to about 50 hours. The standard was 50 hours.
- Example 1 A container containing aluminum oxide melt is installed in an electric furnace maintained in a nitrogen atmosphere, and an Ir wire and an Ir-40 mass% Rh wire as an element wire and a metal mainly composed of hafnium oxide as an insulator Through the hole of the insulating tube made of oxide, the ends of the Ir wire and Ir-40 mass% Rh wire were welded to form a temperature measuring contact, and the strand and the insulating tube were inserted into the protective tube made of Ir.
- Thermocouple having a structure (hereinafter referred to as “Ir (protection tube) / metal oxide mainly composed of hafnium oxide (insulation tube) / Ir and Ir-40% by mass Rh (elementary wire)”).
- the protective tube had an outer diameter of 8 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. The relationship between elapsed time and temperature is shown in FIG. Temperature measurement was performed under the above conditions, and the temperature measurement was terminated when 50 hours had passed since reaching 2000 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Thermocouple having a structure of Mo (protection tube) / metal oxide (insulation tube) / Ir and Ir-40 mass% Rh (element wire) mainly composed of hafnium oxide in an electric furnace maintained in a nitrogen atmosphere was inserted sideways, the temperature was raised to 2000 ° C., and the temperature inside the furnace was measured.
- the protective tube had an outer diameter of 6.4 mm and a wall thickness of 0.9 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was performed under the above conditions, and the temperature measurement was terminated when 50 hours had passed since reaching 2000 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- thermocouple having a structure of W (protection tube) / metal oxide (insulating tube) / Ir and Ir-40 mass% Rh (elementary wire) mainly composed of hafnium oxide in an electric furnace kept in a vacuum.
- the furnace was inserted vertically and heated to 1900 ° C. to measure the temperature in the furnace.
- the protective tube had an outer diameter of 6.2 mm and a wall thickness of 0.8 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1900 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- thermocouple having a structure of Ta (protection tube) / metal oxide (insulation tube) / Ir and Ir-40 mass% Rh (elementary wire) mainly composed of hafnium oxide in an electric furnace kept in a vacuum. It was inserted vertically and heated to 1950 ° C. to measure the temperature in the furnace.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1950 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 5 In an electric furnace maintained in an Ar atmosphere, Ir (protection tube) / metal oxide mainly composed of hafnium oxide (insulation tube) / W-5 mass% Re and W-26 mass% Re (wire) A thermocouple having a structure was inserted vertically, and the temperature inside the furnace was measured by raising the temperature to 1900 ° C.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1900 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 6 In an electric furnace maintained in an Ar atmosphere, Mo (protection tube) / metal oxide mainly composed of hafnium oxide (insulation tube) / W-5 mass% Re and W-26 mass% Re (wire) A thermocouple having a structure was inserted vertically, and the temperature inside the furnace was measured by raising the temperature to 1900 ° C.
- the protective tube had an outer diameter of 6.4 mm and a wall thickness of 0.9 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1900 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 7 In an electric furnace maintained in an Ar atmosphere, W (protective tube) / metal oxide (insulating tube) mainly composed of hafnium oxide / W-5 mass% Re and W-26 mass% Re (wire) A thermocouple having a structure was inserted vertically, and the temperature inside the furnace was measured by raising the temperature to 1900 ° C.
- the protective tube had an outer diameter of 6.2 mm and a wall thickness of 0.8 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1900 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 8 In an electric furnace maintained in an Ar atmosphere, Ta (protection tube) / metal oxide mainly composed of hafnium oxide (insulation tube) / W-5 mass% Re and W-26 mass% Re (wire) A thermocouple having a structure was inserted vertically, and the temperature inside the furnace was measured by raising the temperature to 1900 ° C.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1900 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 9 It has a structure of Pt-10% by mass Rh (protection tube) / metal oxide (insulating tube) mainly composed of hafnium oxide / Pt-13% by mass Rh and Pt (elementary wire) in an electric furnace in an air atmosphere.
- An R thermocouple was inserted vertically, the temperature was raised to 1500 ° C., and the temperature inside the furnace was measured.
- the outer diameter of the protective tube is 6 mm, and the thickness of the protective tube is 1 mm.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1500 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 10 In an electric furnace in the air atmosphere, Pt-10 mass% Rh (metal protective tube) / metal oxide (insulating tube) mainly composed of hafnium oxide / Pt-13 mass% Rh and oxide dispersion strengthened platinum (elementary wire) R thermocouple having a structure of) was inserted vertically and the temperature was raised to 1500 ° C. to measure the temperature in the furnace.
- the outer diameter of the protective tube is 6 mm, and the thickness of the protective tube is 1 mm.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1500 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 11 In an electric furnace in an air atmosphere, Pt-10 mass% Rh (protection tube) / metal oxide mainly composed of hafnium oxide (insulating tube) / Pt-30 mass% Rh and Pt-6 mass% Rh (elementary wire)
- the thermocouple B having the structure (1) was inserted vertically and the temperature was raised to 1700 ° C. to measure the temperature in the furnace.
- the outer diameter of the protective tube is 6 mm, and the thickness of the protective tube is 1 mm.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was performed under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1700 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 12 In an electric furnace maintained in an Ar atmosphere, Ir (protection tube) / metal oxide mainly composed of hafnium oxide (insulation tube) / Pt-20 mass% Rh and Pt-40 mass% Rh (elementary wire) A thermocouple having a structure was inserted vertically, and the temperature inside the furnace was measured by raising the temperature to 1800 ° C.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.2 mm, and a two-hole tube with an inner diameter of 0.9 mm was provided in order to insert the wire inside the insulating tube.
- the material of the insulating tube contains 0.16% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulating tube were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1800 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- Example 13 In an electric furnace maintained in an Ar atmosphere, Ir wires and Ir-40 mass% Rh wires are used as the strands, and the ends of the Ir wires and Ir-40 mass% Rh wires are welded to form a temperature measuring contact. And inserted in a protective tube made of Ir and filled with a metal oxide powder mainly composed of hafnium oxide as an insulator between the strand and the protective tube (hereinafter referred to as “Ir (protective tube) / oxidation”). Insert a thermocouple having a metal oxide (insulator) containing hafnium as a main component / Ir and Ir-40% by mass Rh (elementary wire) ”in the vertical direction and raise the temperature to 1900 ° C.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulator a powder having an average particle diameter of 100 ⁇ m or less by a laser diffraction / scattering method was used.
- the material of the insulator contains 0.30% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, the content of each element of Al, Fe, Si and Ti is 100 mass ppm or less, the content of C The amount is 10 mass ppm or less.
- the wire diameter of each strand is 0.5 mm. Further, after the strands and the insulator were inserted into the protective tube, no wire drawing was performed. Temperature measurement was carried out under the above conditions, and the temperature measurement was terminated when 50 hours had passed after reaching 1900 ° C., but no thermoelectromotive force abnormality of the thermocouple occurred during temperature measurement.
- thermocouple having a structure of Ir (protection tube) / aluminum oxide (insulation tube) / Ir and Ir-40 mass% Rh (elementary wire) was inserted vertically into an electric furnace maintained in an Ar atmosphere. The temperature inside the furnace was measured by raising the temperature to 0 ° C.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.0 mm, and a two-hole tube with an inner diameter of 0.8 mm was provided to insert the strand into the insulating tube.
- the wire diameter of each strand is 0.5 mm.
- thermocouple was confirmed by SEM, disconnection was confirmed at Ir-40 mass% Rh (elementary wire) as shown in FIG.
- deformation and discoloration were confirmed in the aluminum oxide (insulating tube) near the temperature measuring contact.
- EDX energy dispersive X-ray spectroscopic analysis
- thermocouple having a structure of Ir (protection tube) / hafnium oxide (insulation tube) / Ir and Ir-40% by mass Rh (elementary wire) was inserted vertically into an electric furnace kept in a vacuum, and the temperature was 1950 ° C. The temperature inside the furnace was measured.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.0 mm, and a two-hole tube with an inner diameter of 0.8 mm was provided to insert the strand into the insulating tube.
- the material of the insulating tube contains 0.30% by mass of zirconium oxide in terms of the amount of zirconium in hafnium oxide, and 33 mass ppm of C.
- the wire diameter of each strand is 0.5 mm.
- the wire drawing was not performed after inserting the strand and the insulating tube into the protective tube.
- Temperature measurement was performed under the above-described conditions, and the temperature measurement was terminated when 50 hours had elapsed after reaching 1950 ° C., and the temperature was lowered. At that time, a thermoelectromotive force abnormality occurred in the thermocouple during the temperature drop. When the inside of the thermocouple was confirmed, disconnection was confirmed in Ir-40 mass% Rh (elementary wire).
- thermocouple having a structure of Ir (protection tube) / hafnium oxide (insulation tube) / Ir and Ir-40% by mass Rh (elementary wire) was inserted vertically into an electric furnace maintained in an Ar atmosphere. The temperature inside the furnace was measured by raising the temperature to 0 ° C.
- the protective tube had an outer diameter of 6 mm and a wall thickness of 1 mm, and the inside was filled with Ar and sealed.
- the insulating tube had an outer diameter of 3.0 mm, and a two-hole tube with an inner diameter of 0.8 mm was provided to insert the strand into the insulating tube.
- the material of the insulating tube 1800 mass ppm of Al and 300 ppm of Si are contained in hafnium oxide.
- the wire diameter of each strand is 0.5 mm.
- the wire drawing was not performed after inserting the strand and the insulating tube into the protective tube.
- Temperature measurement was carried out under the above conditions, and temperature measurement was interrupted when 50 hours had elapsed after reaching 1900 ° C., and the temperature was lowered. At that time, a thermoelectromotive force abnormality occurred in the thermocouple during the temperature drop.
- disconnection was confirmed in Ir-40 mass% Rh (elementary wire).
- SEM scanning electron microscope
- thermocouple having a structure of Mo (protection tube) / hafnium oxide (insulator) / Ir and Ir-40 mass% Rh (elementary wire).
- the outer diameter of the protective tube is 4.8 mm, and the thickness of the protective tube is 0.5 mm.
- As the insulator a powder having a particle size of 0.1 mm or less was used.
- the wire diameter of each strand is 0.5 mm.
- the wire drawing process was implemented on various conditions, most of them were disconnected during the process.
- the continuity between the strands was confirmed, and the case where the continuity could not be taken was judged as a disconnection.
- Conduction confirmation between the strands was carried out, and regarding the thermocouple confirmed to be conducting, an attempt was made to measure the temperature inside the furnace by inserting the thermocouple vertically into an electric furnace maintained in an Ar atmosphere. A thermoelectromotive force abnormality occurred during warming, and the heating and measurement were interrupted. When conducting the continuity check between the strands, it was determined that the continuity was broken because the continuity could not be obtained.
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Abstract
Description
窒素雰囲気に保たれた電気炉内に酸化アルミニウム融液を入れた容器を設置し、素線としてのIr線及びIr-40質量%Rh線を、絶縁物としての酸化ハフニウムを主成分とする金属酸化物からなる絶縁管の穴に通し、Ir線及びIr-40質量%Rh線の端部同士を溶接して測温接点を形成し、素線及び絶縁管をIrからなる保護管に挿入した構造(以降、「Ir(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Ir及びIr-40質量%Rh(素線)」のように表記する。)を有する熱電対を縦向きに挿入し、2000℃に昇温して酸化アルミニウム融液直上付近の温度測定を行った。保護管は外径8mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。経過時間と温度との関係を図3に示した。前記の条件で測温を実施し、2000℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
窒素雰囲気に保たれた電気炉内に、Mo(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を横向きに挿入し、2000℃に昇温して炉内の温度測定を実施した。保護管は外径6.4mm、肉厚が0.9mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、2000℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
真空に保たれた電気炉内に、W(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6.2mm、肉厚が0.8mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
真空に保たれた電気炉内に、Ta(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を縦向きに挿入し、1950℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1950℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内に、Ir(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/W-5質量%Re及びW-26質量%Re(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内に、Mo(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/W-5質量%Re及びW-26質量%Re(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6.4mm、肉厚が0.9mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内に、W(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/W-5質量%Re及びW-26質量%Re(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6.2mm、肉厚が0.8mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内において、Ta(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/W-5質量%Re及びW-26質量%Re(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
大気雰囲気の電気炉内に、Pt-10質量%Rh(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Pt-13質量%Rh及びPt(素線)の構造を有するR熱電対を縦向きに挿入し、1500℃に昇温して炉内の温度測定を実施した。保護管の外径は6mmであり、保護管の肉厚は1mmである。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1500℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
大気雰囲気の電気炉内に、Pt-10質量%Rh(金属保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Pt-13質量%Rh及び酸化物分散強化白金(素線)の構造を有するR熱電対を縦向きに挿入し、1500℃に昇温して炉内の温度測定を実施した。保護管の外径は6mmであり、保護管の肉厚は1mmである。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1500℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
大気雰囲気の電気炉内に、Pt-10質量%Rh(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Pt-30質量%Rh及びPt-6質量%Rh(素線)の構造を有するB熱電対を縦向きに挿入し、1700℃に昇温して炉内の温度測定を実施した。保護管の外径は6mmであり、保護管の肉厚は1mmである。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1700℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内に、Ir(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁管)/Pt-20質量%Rh及びPt-40質量%Rh(素線)の構造を有する熱電対を縦向きに挿入し、1800℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.2mmで、絶縁管内部に素線を挿通するため内径0.9mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.16質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1800℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内に、素線としてIr線及びIr-40質量%Rh線を用い、Ir線及びIr-40質量%Rh線の端部同士を溶接して測温接点を形成し、Irからなる保護管に挿入し、素線と保護管との間に絶縁物として酸化ハフニウムを主成分とする金属酸化物の粉末を充填した構造(以降、「Ir(保護管)/酸化ハフニウムを主成分とする金属酸化物(絶縁物)/Ir及びIr-40質量%Rh(素線)」のように表記する。)を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を行った。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁物はレーザー回折・散乱法による平均粒径が100μm以下の粉末を使用した。絶縁物の材質は、酸化ハフニウムにジルコニウムの量で換算して0.30質量%の酸化ジルコニウムを含有し、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下、Cの含有量が10質量ppm以下である。素線の線径はいずれも0.5mmである。また、素線及び絶縁物を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を終了したが、測温中に熱電対の熱起電力異常は発生しなかった。
Ar雰囲気に保たれた電気炉内に、Ir(保護管)/酸化アルミニウム(絶縁管)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.0mmで、絶縁管内部に素線を挿通するため内径0.8mmの2穴管を設けた。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工を実施しなかった。前記の条件で測温を実施したところ、1900℃に到達してから9.1時間経過したところで熱起電力異常が発生したため、測温を中断した。熱電対内部をSEMで確認したところ、図4に示すようにIr-40質量%Rh(素線)において断線を確認した。また、測温接点付近の酸化アルミニウム(絶縁管)において、変形、変色を確認した。断線部(図4のA部)をエネルギー分散型特性X線分光分析(EDX)で分析したところ、図5に示すようにAlを含む不純物を検出した。
真空に保たれた電気炉内に、Ir(保護管)/酸化ハフニウム(絶縁管)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を縦向きに挿入し、1950℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.0mmで、絶縁管内部に素線を挿通するため内径0.8mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにジルコニウムの量で換算して0.30質量%の酸化ジルコニウムを含有し、Cを33質量ppm含有する。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工は実施しなかった。前記の条件で測温を実施し、1950℃に到達してから50時間経過したところで測温を終了し、降温を実施した。その際、降温中に熱電対において熱起電力異常が発生した。熱電対内部を確認したところ、Ir-40質量%Rh(素線)において断線を確認した。断線部付近を走査電子顕微鏡(SEM)で観察したところ、図6に示すように、前記素線表面において反応した形跡を確認した。この部分(図6のA部)をエネルギー分散型特性X線分光分析(EDX)で分析したところ、図7に示すようにIr及びRhの他に、C及びHfを検出した。
Ar雰囲気に保たれた電気炉内に、Ir(保護管)/酸化ハフニウム(絶縁管)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を縦向きに挿入し、1900℃に昇温して炉内の温度測定を実施した。保護管は外径6mm、肉厚が1mmで、内部はArを充填して密閉した。絶縁管は外径3.0mmで、絶縁管内部に素線を挿通するため内径0.8mmの2穴管を設けた。絶縁管の材質は、酸化ハフニウムにAlが1800質量ppm、Siが300ppm含有する。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、伸線加工は実施しなかった。前記の条件で測温を実施し、1900℃に到達してから50時間経過したところで測温を中断し、降温を実施した。その際、降温中に熱電対において熱起電力異常が発生した。熱電対内部を確認したところ、Ir-40質量%Rh(素線)において断線を確認した。断線部付近を走査電子顕微鏡(SEM)で観察したところ、図8に示すように、前記素線表面において反応した形跡を確認した。断線部周辺(図8のA部)をエネルギー分散型特性X線分光分析(EDX)で分析したところ、図9に示すようにIr及びRhの他に、Al及びSiを検出した。
Mo(保護管)/酸化ハフニウム(絶縁物)/Ir及びIr-40質量%Rh(素線)の構造を有する熱電対を形成後、伸線加工による熱電対の作製を実施した。保護管の外径は4.8mmであり、保護管の肉厚は0.5mmである。絶縁物は粒径が0.1mm以下の粉末を使用した。素線の線径はいずれも0.5mmである。また、素線及び絶縁管を保護管内に挿入後、種々の条件で伸線加工を実施したが、そのほとんどが加工中に断線した。断線は、素線同士の導通確認を実施し、導通がとれない場合を断線と判断した。素線同士の導通確認を実施し、導通が確認された熱電対に関して、Ar雰囲気に保たれた電気炉に熱電対を縦向きに挿入して炉内の温度測定を実施しようとしたが、昇温中において熱起電力異常が発生し、昇温及び測定を中断した。素線同士の導通確認を実施したところ、導通がとれなくなっていたため、断線していると判断した。
12 Ir線
13 Ir・Rh線
14 測温接点
5,15 絶縁物
5a,5b 細長孔
16 保護管
16a 封止部
17a,17b 酸素バリア膜
Claims (9)
- 少なくとも保護管と素線とを有する熱電対であって、
前記保護管と前記素線とが絶縁物によって絶縁されており、
前記絶縁物が、粉末若しくは成形体のいずれか一方又は両方であり、酸化ジルコニウム、酸化ハフニウム又はジルコニウムとハフニウムとの複合酸化物の少なくとも一種からなることを特徴とする熱電対。 - 前記絶縁物は、Al、Fe、Si及びTiの各元素の含有量が100質量ppm以下であり、かつ、Cの含有量が10質量ppm以下であることを特徴とする請求項1に記載の熱電対。
- 前記素線の表面が、酸素バリア膜で被覆されており、該酸素バリア膜の厚さが20nm以上800nm以下であることを特徴とする請求項1又は2に記載の熱電対。
- 前記素線が、Ir、Pt、Rh、Mo、Re、Nb、Ta及びWから選ばれる元素の一種又は二種からなることを特徴とする請求項1~3のいずれか一つに記載の熱電対。
- 前記素線の表面を被覆する酸素バリア膜は主成分として酸化物を含み、該酸化物の酸素と結合する元素が、Hf若しくはZrのいずれか一方又はその両方であることを特徴とする請求項3又は4に記載の熱電対。
- 前記保護管の外表面の全体若しくはその一部分、又は、前記保護管の内表面の全体若しくはその一部分、の少なくともいずれか一方が、酸素バリア膜で被覆されており、該酸素バリア膜の厚さが20nm以上800nm以下であることを特徴とする請求項1~5のいずれか一つに記載の熱電対。
- 前記保護管が、Ir、Pt、Rh、Ru、Mo、Re、Nb、Ta及びWから選ばれる元素の一種又は二種を用いて形成されていることを特徴とする請求項1~6のいずれか一つに記載の熱電対。
- 前記保護管の外表面又は内表面を被覆する酸素バリア膜は主成分として酸化物を含み、該酸化物の酸素と結合する元素が、Hf若しくはZrのいずれか一方又はその両方であることを特徴とする請求項6又は7に記載の熱電対。
- 請求項1~8のいずれか一つに記載の熱電対の製造方法であって、
前記素線と絶縁物とを、前記保護管内に挿入した後、伸線加工を行わないことを特徴とする熱電対の製造方法。
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US10918437B2 (en) | 2015-05-18 | 2021-02-16 | Biosense Webster (Israel) Ltd. | Catheter with coaxial thermocouple |
CN113288403A (zh) * | 2015-05-18 | 2021-08-24 | 韦伯斯特生物官能(以色列)有限公司 | 具有共轴热电偶的导管 |
CN113288403B (zh) * | 2015-05-18 | 2024-04-16 | 韦伯斯特生物官能(以色列)有限公司 | 具有共轴热电偶的导管 |
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JP7308699B2 (ja) | 2019-09-03 | 2023-07-14 | 東京エレクトロン株式会社 | 熱電対構造、熱処理装置及び熱電対構造の製造方法 |
US11815407B2 (en) | 2019-09-03 | 2023-11-14 | Tokyo Electron Limited | Thermocouple structure, heat treatment apparatus, and method of manufacturing thermocouple structure |
Also Published As
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US20160231181A1 (en) | 2016-08-11 |
JPWO2015041315A1 (ja) | 2017-03-02 |
JP6578209B2 (ja) | 2019-09-18 |
US10281337B2 (en) | 2019-05-07 |
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