WO1993004504A1 - Detecteur de temperature a thermocouple - Google Patents

Detecteur de temperature a thermocouple Download PDF

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Publication number
WO1993004504A1
WO1993004504A1 PCT/AU1992/000382 AU9200382W WO9304504A1 WO 1993004504 A1 WO1993004504 A1 WO 1993004504A1 AU 9200382 W AU9200382 W AU 9200382W WO 9304504 A1 WO9304504 A1 WO 9304504A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermocouple
ceramic compound
metal
sheath
glass
Prior art date
Application number
PCT/AU1992/000382
Other languages
English (en)
Inventor
Noel Arthur Burley
Original Assignee
Nicrobell Pty. Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nicrobell Pty. Limited filed Critical Nicrobell Pty. Limited
Publication of WO1993004504A1 publication Critical patent/WO1993004504A1/fr

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Classifications

    • 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
    • G01K1/10—Protective devices, e.g. casings for preventing chemical attack
    • 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
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device

Definitions

  • thermocouples thermocouples, thermocouple structures, thermocouple sheathing, and to protection devices containing a thermocouple.
  • this invention relates to a novel improved design and structure of a thermocouple intended for application at high temperatures above, say 1000°C.
  • this invention relates to high-temperature structural fine ceramics for use in the manufacture of thermocouple structures.
  • this invention relates to novel improved thermocouple structures intended specifically for use in the measurement of the temperatures of hot molten glass in the manufacture of a wide range of glass materials, products and components.
  • the thermocouples of the invention are primarily of the mineral-insulated integrally metal-sheathed (MIMS) structure.
  • Figure 1 represents a longitudinal section of a typical prior art thermocouple of the Pt-Rh/Pt type
  • Figure 2 represents a perspective view of a conventional MIMS-type thermocouple
  • Figure 3 is a bar graph comparing modulus of rupture for four different ceramic materials.
  • Figure 4 is a diagrammatic representation of a longitudinal section of a thermocouple according to this invention.
  • thermocouple sensor structures The measurement of the temperature of hot molten glass presents singular technical and economic difficulties due to a range of diverse factors. These factors include the very high industrial temperatures involved, the high viscosity and abrasiveness of flowing molten glass at these temperatures, the chemical reactivity of both the glass itself and also of the combustion atmosphere in which it is heated, and the high cost of the rare-metal materials of construction of the conventional thermocouple sensor structures presently employed.
  • glass can be used to describe many substances which possess the physical characteristics of a liquid but the rigidity of a solid. Glass, like most liquids, has a random molecular structure particularly when hot. When most liquids solidify or “freeze” these molecules normally are regimented into precise crystallographic arrays. In the manufacture of glass, during subsequent cooling, this freezing does not take place; the viscosity simply rises with falling temperature to a stage where the molecules of the super-cooled liquid cannot move to form a regular crystal structure. Even when still very hot, say at 1200°C, the viscosity of the flowing molten mass remains relatively quite high, and it can exert a significant force on any object located in its path. This includes elongated cylindrical objects such as sheaths housing thermocouples. Thus a thermocouple sheath material capable of resisting the high bending moment forces exerted by the hot flowing glass must exhibit high values of strength, toughness and creep resistance.
  • thermocouples of the platinum-rhodium versus platinum (Pt- Rh/Pt) variety designated type R (13 wt-% Rh) or type S (10 wt-% Rh) by the Instrument Society of America (ISA)
  • ISA Instrument Society of America
  • thermocouple A typical such thermocouple is illustrated in Figure 1, in which the following features are identified:
  • thermocouples The number of failures of alumina-sheathed rare-metal thermocouples, due to mechanical stress and/or chemical contamination, is reportedly reduced by the use of such thimbles .
  • Such sensor assemblies may contain multiple thermocouples having measuring-thermojunctions so arranged as to enable temperatures to be measured at various depths in the glass (see Figure 1) .
  • the high temperatures and aggressive glass conditions make it necessary for alumina- sheathed Pt-Rh/Pt thermocouples to be protected by Pt or Pt-alloy thimbles below the glass line.
  • thermocouples incorporating Pt-alloy thimbles and thermocouples it is common practice to attach a shortened platinum thimble to a co-linear extension tube fabricated from a conventional base-metal alloy like Inconel (see Figure 1) .
  • This extension tube passes up through the combustion gas space above the glass line and through the wall or ceiling of the furnace to the cooler ambient environment outside.
  • Conventional base-metal alloys like Inconel
  • the extension tube may even fail prematurely by high-temperature corrosion, particularly near the junction with the rare-metal thimble. Thus the life of the whole thermocouple assembly can be terminated prematurely.
  • MIMS cable or of individual MIMS thermocouple sensor structures begins with matched thermocouple wires surrounded by non- compacted mineral oxide powder held within a metal tube.
  • the tube is reduced in diameter by the required amount and the insulation is compacted around the wires.
  • the conventional product of MIMS structure is illustrated diagrammatically in Figure 2.
  • 2.1 is the integral sheath, usually made of stainless steel or Inconel;
  • 2.2 is the mineral insulation, usually a mixture of mineral oxides essentially of about 96 wt.-% MgO and 4 wt.-% Si0 2 ;
  • 2.3 are the thermoelement conductor wires usually of the ISA (Instrument Society of America) type K variety.
  • the conventional sheath materials will not withstand exposure in molten glass and in the associated combustion atmosphere at the temperatures involved (up to about 1200°C) .
  • the conventional thermocouple conductor wires - ISA type K - will likewise not withstand the highest temperatures and longest times encountered in the glass industry.
  • thermoelement conductor wires can be contaminated by chemical elements which thermally diffuse through the compacted insulant material from dissimilar sheath alloys.
  • the resultant changes in the chemical compositions of the conductor alloys can cause substantial changes in their thermoelectromotive forces.
  • Such changes in thermal emf are analogous with and algebraically additive to those caused by the high-temperature oxidation of these alloys.
  • the thermoelement conductor wires, particularly the negative wire may fail mechanically because of substantial alternating strains imposed during thermal cycling. These strains are caused primarily by longitudinal stresses which arise because of substantially different temperature coefficients of linear expansion of the thermoelements and of dissimilar sheath materials.
  • thermoelectric instability the principal problem in the measurement of high temperatures using a thermocouple of conventional MIMS construction is thermoelectric instability, hence measurement uncertainty. It is equally clear that this thermal emf instability results primarily from the use of dissimilar and unsuitable alloys for both sheath and thermoelement conductors. This problem has arisen because sheath and thermoelement materials have hitherto been chosen independently of each other to match, respectively, the environment of exposure and the calibration of existing pyrometric instrumentation. In contrast to the prior art, the MIMS thermocouple of the present invention has been designed as a truly integral system.
  • thermoelement conductor alloys known as NIOBELL- P (positive) and NIOBELL-N (NIOBELL is a trade mark of Nicrobell Pty. Ltd.) or, alternatively, standard thermoelement conductors which are ISA type N alloys .
  • thermocouple cable is the subject of the above-mentioned patent specifications 80105/87 and 12149/88. These specifications set out the conceptual nature and inventive rationale of the above type N MIMS systems; they do not, however, make any reference to the specific thermocouple structures nor the thermocouple sheathing and protection devices for molten glass temperatures which are claimed as novel in the present specification. For all these reasons, in particular the prohibitive cost of the conventional glass thermocouple described above, it is essential that novel thermocouple concepts, designs and structures be introduced.
  • thermocouple in which the sensor sheath is made of NICROBELL, FECRALY, NICRALY or COCRALY base metal alloy, and the sheath is coated with a refractory metal oxide or compound which is overcoated with a layer of platinum or platinum alloy.
  • the thermocouples of this specification still require precious metal, and therefore suffer a cost disadvantage.
  • the present invention therefore seeks to provide a thermocouple for use at high temperature which reduces or avoids the use of precious metals.
  • thermocouple suitable for use at high temperatures in a hostile environment such as molten glass, comprising thermocouple conductors held within a thermocouple sheath, wherein the thermocouple is contained within a protection tube which comprises a ceramic compound having an appropriate combination of intrinsic strength, toughness, and chemical stability at high temperature.
  • the novel glass-temperature thermocouple of this invention may be of the integrally metal-sheathed mineral- insulated (MIMS) format and structure.
  • the MIMS format which features improved materials and structure, enables optimal achievement of the necessary performance characteristics.
  • the present invention provides a mineral-insulated, metal-sheathed (MIMS) thermocouple suitable for use at high temperatures in a hostile environment such as molten glass, comprising thermocouple conductors surrounded by mineral insulation held within a thermocouple sheath, wherein the MIMS thermocouple is contained within a protection tube which comprises a fine structural ceramic compound having high intrinsic strength, toughness, and chemical stability at high temperature.
  • the protection tube is coated with a layer of a protective material selected from the group consisting of a rare metal, a rare metal alloy, a refractory metal oxide, or a metal aluminide. A combination of two or more of these protective materials may be used.
  • a layer of compacted ceramic oxide insulant between the thermocouple and the protection tube.
  • the fine structural ceramic compound is selected from the group consisting of silicoaluminoxy- nitrides (Sialons), amorphous alumina, partially stabilized zirconia (PSZ) , silicon nitride, and silicon carbide. Most preferably the ceramic compound is a Sialon, PSZ, or silicon nitride. In some circumstances where the conditions obtaining in the molten glass during manufacture are not overly severe, for example where glass temperatures and flow rates are not excessively high, a less preferred option involves the use of conventional ceramic compounds such as pure recrystallised alumina for thermocouple protection tubes.
  • the MIMS thermocouple sheath is made of the nickel-base alloy NICROBELL.
  • thermocouple conductor alloy is selected from the group consisting of the nickel-base alloys NIOBELL and type N alloys.
  • the invention provides for use in particularly demanding conditions a thermocouple (which may be MIMS) of the rare metal type, selected from the group consisting of ISA types R, S or B, wherein the thermocouple sheath is contained within a protection tube which comprises a fine structural ceramic compound as defined above.
  • thermocouple system and specific sensor structures of the present invention are very well suited to glass-temperature thermocouple sensors.
  • the new concepts of the present invention feature relatively inexpensive base-metal alloys for the thermocouple conductors and structural fine ceramic materials for the protection tubes.
  • the ceramic sheath materials chosen show an optimum combination of strength, toughness and high chemical stability at the high-temperatures and under the aggressive environmental conditions prevailing within the glass furnace during the manufacturing processes involved.
  • the base-metal thermocouple incorporated in the design and structure of the novel thermocouple sensor shows ultra-high thermoelectric stability, such as is exhibited by rare-metal Pt-alloy thermocouples, over the range of temperatures involved.
  • thermocouple alloys and the protective sheath alloys NICROBELL may not provide, per se, the very high environmental stability and longevity that would be demanded for the longest of the glass furnace campaigns that can be envisaged.
  • a protection tube material which shows the required high values of thermomechanical properties and resistance to high temperature corrosion that would be demanded.
  • Such a protection tube material is one of the family of newly developed fine structural ceramic compounds. These materials have intrinsic high strength and toughness at high temperatures as well as high chemical stability. Examples of these fine structural ceramics include amorphous alumina A1.0 3 , partially stabilised zirconia Y 2 0 3 - Zr0 2 (commonly known as PSZ) , silicon nitride Si 3 N 4 , silicon carbide SiC, and the silicoaluminoxynitrides Si a Al b O c N d (commonly known as 'Sialon'). Of these compounds Y 2 0 3 -
  • Zr0 2 , Si 3 N 4 and Sialon are particularly suitable for use in the present invention.
  • PSZ shows high values of strength and toughness because of the presence of small quantities of oxides such as CaO and Zr0 2 which stabilise the high-temperature cubic crystal structure.
  • strengths can be increased up to about 700 MPa.
  • si.N 4 has high strength over a wide temperature range, good thermal shock resistance, and high resistance to wear and corrosion.
  • Components consisting of silicon nitride are more resistant (than metals and oxide ceramics such as alumina) to high temperatures, thermal shock, erosion and chemical degradation.
  • a structural ceramic material particularly preferred for the requirements of the present invention is Sialon. This material is, in fact, a chemical 'alloying' of some of the other ceramic compounds mentioned above. The phase relationships of the ceramic 'alloy' system
  • Si 3 N 4 -Si0 2 -Al 2 0 3 -AlN reveal a compositional zone of general formula Si 6 _ ⁇ Al ⁇ O ⁇ N 8 _ ⁇ known as beta-Sialon.
  • beta-Sialon Although there are other Sialon-type compounds possible, most effort has been focussed on the fabrication of beta-Sialon because of its superior creep and oxidation resistance properties at high temperature.
  • thermocouple sensor of this example is fabricated using existing manufacturing procedures. They begin with thermoelectrically matched thermoelement wires fabricated in the form of a tri-level thermocouple (of the NIOBELL or ISA type N variety) surrounded by non-compacted ceramic oxide insulating powder held within a metallic alloy tube of NICROBELL alloy. By rolling, swageing, drawing, or other suitable mechanical reduction processes the alloy tube may be reduced in diameter until the insulation powder is compacted around the thermocouple wires. The manufacturing process parameters are adjusted so that the ratios of sheath diameter to wire-size and to sheath-wall thickness offer an optimal balance between minimum wall-thickness for adequate life and for strength, and also suitable insulation spacing for effective insulation resistance at elevated temperatures. A most important feature of the fabrication process is that considerable attention is given to the initial cleanliness and chemical purity of the components and to retention of a high degree of cleanliness and dryness particularly of the insulant throughout fabrication.
  • thermocouple sensor In this example, the mode of manufacture and design of the thermocouple sensor, per se, is the same as in Example 1.
  • the structural ceramic sheathing tube (item 3 in Figure 4) may not provide the very high environmental stability and longevity that would be demanded for the longest of the glass furnace manufacturing campaigns that can eventuate.
  • a suitable relatively thin but strongly adherent coating to the protection tube of a refractory metal, alloy, or chemical compound which will satisfactorily withstand the extreme conditions described above.
  • Suitable coatings include an optimal thickness of a rare metal, a rare metal alloy, a refractory metal oxide such as alumina, or a metal aluminide, etc. The thickness of such a metal coating is much less, of the order of one- tenth, of that required for the corresponding thimble of the prior art.
  • Other types of protective coating would also be suitable, and would be known to the person skilled in the art.
  • the methods of coating deposition would include electrodeposition from aqueous solutions or fused salts, vacuum or air thermal plasma spraying, or other thermal spraying, physical or chemical vapour deposition, etc.
  • Other suitable deposition processes will be known to the person skilled in the art.
  • thermocouple sensor In this example the general mode of manufacture and design of the thermocouple sensor is the same as in Example 1 or Example 2. In this case, however, which is also germane to the very most extreme conditions of high temperatures and extended production campaigns that can be encountered in a glass furnace, it is necessary to revert to the use of standard ISA types B, R or S thermocouples. Here it is not feasible to compact the mineral insulant by a tube reduction process, but rather an optional process such as tamping is employed to avoid damage to the rare-metal thermocouple assembly.
  • Example 4 In this example the general mode of manufacture and design of the thermocouple sensor is the same as in Example 1, Example 2, or Example 3.
  • thermocouple protection tube chosen is fabricated from a group comprising conventional ceramic compounds such as pure recrystallised alumina.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)

Abstract

Un thermocouple pouvant être utilisé à des températures élevées dans un environnement hostile tel que du verre fondu, et comprenant des conducteurs de thermocouple maintenus dans une gaine de thermocouple, est contenu dans un tube protecteur qui comprend un composé céramique pouvant être un composé céramique classique ou un composé céramique de structure fine. Le tube de protection peut être recouvert d'une couche d'un matériau protecteur choisi à partir d'un ou plusieurs éléments du groupe composé d'un métal rare, d'un alliage métallique rare, d'un oxyde métallique réfractaire et d'un aluminure métallique.
PCT/AU1992/000382 1991-08-16 1992-07-27 Detecteur de temperature a thermocouple WO1993004504A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPK779491 1991-08-16
AUPK7794 1991-08-16
AUPL189292 1992-04-14
AUPL1892 1992-04-14

Publications (1)

Publication Number Publication Date
WO1993004504A1 true WO1993004504A1 (fr) 1993-03-04

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PCT/AU1992/000382 WO1993004504A1 (fr) 1991-08-16 1992-07-27 Detecteur de temperature a thermocouple

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995032400A2 (fr) * 1994-05-24 1995-11-30 Alcan International Limited Procede de commande de fours de calcination rotatifs et systeme de commande associe
US5523957A (en) * 1993-07-15 1996-06-04 Alcan International Limited Process for controlling rotary calcining kilns, and control system therefor
EP0764837A1 (fr) * 1995-09-25 1997-03-26 Isuzu Ceramics Research Institute Co., Ltd. Structure de thermocouple
EP0939292A1 (fr) * 1998-02-27 1999-09-01 Sollac Dispositif et procédé de mesure en continu de l'usure d'une paroi de récipient métallurgique
CN102636277A (zh) * 2012-04-10 2012-08-15 巨石集团有限公司 一种用于玻纤通路玻璃液测温的新型热电偶及其使用方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826625A (en) * 1954-08-30 1958-03-11 Charles M Macdonald Thermo-couple
US4060095A (en) * 1975-08-23 1977-11-29 Koransha Co., Ltd. Thermocouple protecting tube
US4135538A (en) * 1976-11-30 1979-01-23 Koransha Co., Ltd. Thermocouple protecting tube
US4430518A (en) * 1981-11-30 1984-02-07 Denki Kagaku Kogyo Kabushiki Kaisha Protecting tube for thermocouple
FR2590980A1 (fr) * 1985-12-03 1987-06-05 Thermocoax Cie Thermocouple pour la mesure de temperatures elevees dans des milieux corrosifs
DE3708844A1 (de) * 1986-03-18 1987-09-24 Hitachi Metals Ltd Schutzrohr fuer ein thermoelement und verfahren zu seiner herstellung
WO1988002106A1 (fr) * 1986-09-08 1988-03-24 Commonwealth Scientific And Industrial Research Or Cable a thermocouple stable a gaine en metal
AU4611189A (en) * 1988-12-22 1990-06-28 Clive Lindsay Ragless Flexible high temperature thermocouple
WO1990009682A1 (fr) * 1989-02-17 1990-08-23 Nicrobell Pty Limited Capteur pyrometrique thermoelectrique

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826625A (en) * 1954-08-30 1958-03-11 Charles M Macdonald Thermo-couple
US4060095A (en) * 1975-08-23 1977-11-29 Koransha Co., Ltd. Thermocouple protecting tube
US4135538A (en) * 1976-11-30 1979-01-23 Koransha Co., Ltd. Thermocouple protecting tube
US4216028A (en) * 1976-11-30 1980-08-05 Koransha Co., Ltd. Thermocouple protecting tube
US4430518A (en) * 1981-11-30 1984-02-07 Denki Kagaku Kogyo Kabushiki Kaisha Protecting tube for thermocouple
FR2590980A1 (fr) * 1985-12-03 1987-06-05 Thermocoax Cie Thermocouple pour la mesure de temperatures elevees dans des milieux corrosifs
DE3708844A1 (de) * 1986-03-18 1987-09-24 Hitachi Metals Ltd Schutzrohr fuer ein thermoelement und verfahren zu seiner herstellung
WO1988002106A1 (fr) * 1986-09-08 1988-03-24 Commonwealth Scientific And Industrial Research Or Cable a thermocouple stable a gaine en metal
AU4611189A (en) * 1988-12-22 1990-06-28 Clive Lindsay Ragless Flexible high temperature thermocouple
WO1990009682A1 (fr) * 1989-02-17 1990-08-23 Nicrobell Pty Limited Capteur pyrometrique thermoelectrique

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5523957A (en) * 1993-07-15 1996-06-04 Alcan International Limited Process for controlling rotary calcining kilns, and control system therefor
WO1995032400A2 (fr) * 1994-05-24 1995-11-30 Alcan International Limited Procede de commande de fours de calcination rotatifs et systeme de commande associe
WO1995032400A3 (fr) * 1994-05-24 1996-01-18 Alcan Int Ltd Procede de commande de fours de calcination rotatifs et systeme de commande associe
EP0764837A1 (fr) * 1995-09-25 1997-03-26 Isuzu Ceramics Research Institute Co., Ltd. Structure de thermocouple
US5696348A (en) * 1995-09-25 1997-12-09 Isuzu Ceramics Research Institute Co., Ltd. Thermocouple structure
EP0939292A1 (fr) * 1998-02-27 1999-09-01 Sollac Dispositif et procédé de mesure en continu de l'usure d'une paroi de récipient métallurgique
CN102636277A (zh) * 2012-04-10 2012-08-15 巨石集团有限公司 一种用于玻纤通路玻璃液测温的新型热电偶及其使用方法

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