GB2159663A

GB2159663A - Cables including thermoelements

Info

Publication number: GB2159663A
Application number: GB08511525A
Authority: GB
Inventors: Noel Arthur Burley
Original assignee: Bell IRH Pty Ltd
Current assignee: Bell IRH Pty Ltd
Priority date: 1984-05-07
Filing date: 1985-05-07
Publication date: 1985-12-04
Also published as: FR2563937A1; GB2159663B; DE3516260A1; FR2563937B1; CA1238116A; DE3516260C2; GB8511525D0; ATE80223T1; IT8520586A0

Abstract

A compacted mineral insulated integrally sheathed electrically conductive cable utilizing nickel-base alloys includes at least one thermoelement (a) composed of a type N alloy (defined below), and its sheath (b) is composed of an alloy having similar characteristics to the alloy of which the or at least one thermoelement is composed. The electrically conductive cables include thermocouple cables; thermocouple sensors can be made from said thermocouple cables, as can heat detectors, resistive heating elements, and stagnation temperature probes (Fig. 2). Positive type N alloys include, in weight percentages, Cr(14.2 +/- 0.15), Si(1.4 +/- 0.05), Fe(0.1 +/- 0.03), C(0.03 max), Ni(balance). Negative type N alloys include Cr(0.02 max), Si(4,4 + 0.2), Fe(0.1 + 0.)3), C90.03 max), Mg (0.1 +/- 0.05), Ni(balance). <IMAGE>

Description

SPECIFICATION Stable high temperature cables and devices made therefrom This invention reiates to electrically conductive cables, including thermocouple cables, and also includes thermocouple sensors made from the said thermocouple cables. The electrically conductive cables of the invention also include heat detectors and heating elements that are particularly useful at high temperatures.

The invention utilises nickel-base alloys, including those alloys which are used in the thermocouple system designated "type N" by such standards bodies as the Instrument Society of America, the American Society for Testing and Materials, the International Electrotechnical Commission and the British Standards Institution.

In one aspect the invention provides nickel-base thermocouple cables, and nickel-base thermocouple sensor systems made therefrom, having superior oxidation resistance, greater longevity and greater thermoelectric stability under longer time periods and over a range of higher temperatures up to 1 300 C, than existing base-metal cables and sensor systems of the same general kind.

The invention also provides electrically conductive cables including such cables suitable for use as heat detectors and heating elements.

Nickel-base alloys have been used as thermocouples since the early part of this century. One of the commonly used thermocouples is the type K thermocouple (so designated by the Instrument Society of America). The positive type K thermoelement is a nickel-base alloy containing 9.25 percent by weight of chromium and 0.4 percent by weight of silicon, balance essentially nickel. The negative type K thermoelement is a nickel-base alloy containing 3 percent by weight of manganese, 2 percent by weight of aluminium, 1 percent by weight of silicon, with small amounts of iron and cobalt, and the balance essentially nickel.

The type K thermocouple is recommended to be used in an air atmosphere. At the higher temperatures the type K thermocouple fails because of its relatively poor oxidation resistance.

One way in which attempts have been made to overcome this problem is to incorporate the type K thermocouple in a compacted ceramic-insulated thermocouple sensor assembly.

As is well known in the art a first step in the manufacture of such thermocouple sensors is to produce the so-called "MI" (mineral insulated) cable which comprises a sheath containing one or more thermoelement conductor wires electrically insulated from the sheath (and from each other when two or more conductor wires are used) by compacted mineral insulation material.

In the accompanying drawings:- Figure 1 illustrates a typical Ml cable containing two conductor wires (thermoelements); Figure 2 illustrates two basic designs for stagnation temperature probes as more fully discussed below; and Figure 3 illustrates the large negative temperature coefficient of resistance of the densely compacted insulation in heat sensors according to the invention as more fully discussed below.

The MI cable illustrated in Fig. 1 is of a conventional type comprising a sheath 1, compacted insulation 2 and conductor wires (thermoelements) 3.

Further details of the manufacture of Ml cable as illustrated in Fig. 1 are given in Example 1 below.

To make an actual sensor from this cable, the cable is cut and the ends of the conductors are exposed by removing some of the insulation therefrom. The exposed ends of the conductors are then joined to form a thermojunction, which may be accomplished for example by crimping and/or welding.

The thermojunction may simply be left exposed for use in appropriate environments or may be protected by capping the sheath over the thermojunction with or without insulant.

The latter type of thermocouple sensor has come into common use because it isolates the thermocouple wires from environments that may cause rapid deterioration and it provides excellent high-temperature insulation for the thermocouple conductor wires. The sheath can be made of a material which, hopefully, is compatible with the environments and processes in which it is being used and which provides a measure of mechanical protection. There are numerous commercial suppliers of type K thermocouples in compacted ceramic-insulated integrally-sheathed forms.

At temperatures above about 1 050 C known types of compacted ceramic-insulated integrallysheathed cables and thermocouples fail prematurely because of factors such as (i) the materials of which their sheaths are made,such as inconel and stainless steel, fail by deterioration due to oxidation or other accelerated interaction with their gaseous environment; (ii) the individual alloys of the type K thermocouple fail as a result of accelerated oxidation by low-pressure air residual in the compacted ceramic insulation; (iii) the thermoelement conductor wires 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 sheath and thermoelement materials.Some typicaltaverage values of these coefficients of expansion are- Component Material X10-sPC-l (1100"C) sheath stainless steel 20 thermoalloys type K 1 7 (iv) the thermoelement conductor alloys are contaminated by dissolution of extraneous elements received from a different sheath alloy by thermal diffusion through the compacted insulating material. These elements, eg. Mn, Fe, Mo, Cu, cause substantial changes in the thermoelectromotive force of the thermocouple.

(v) the composition of the thermoelement conductor wires is altered by exposure of the thermocouple to prolonged nuclear irradiation, which results in the transmutation of one or more elements in the alloy.

As a result, there is a need for a new integral compacted ceramic-insulated cable suitable as a heating element or for production of thermocouple sensors which is substantially free of the degradative influences described above and which demonstrates enhanced environmental and thermoelectric stability at temperatures significantly in excess of 1 050 C.

It is believed, therefore, that a new compacted ceramic-insulated integrally-sheathed cable, substantially free of degradative influences such as accelerated oxidation, differential thermal stresses, cross-contaminated by diffusion, and transmutations and demonstrating enhanced resistance to environmental interactions and to drifts in thermal e.m.f. and resistivity at temperatures up to 1 300 C in a variety of different atmospheres, is an advancement in the art.

It is also an advancement of the art that certain causes of thermoelectric instability which plague conventional base-metal thermocouple transducers, namely accelerated oxidation, inhomogeneous short-range structural ordering, nuclear transmutations, and magnetic transformations, are virtually eliminated in the new thermocouple sensor of this invention. This is because the compositions of the type N thermoelement conductor wires incorporated in the new integral compacted ceramic-insulated thermocouple sensor are such as to virtually eliminate thermal-emf shifts due to ozidation, in particular internal oxidation, and short-range order, contain no strongly transmuting component elements, and have magnetic transformations below room temperatures.

OBJECTS AND SUMMARY OF INVENTION It is one of the objects of this invention to provide an integral compacted base-metal thermocouple cable and sensor which are thermoelectrically stable up to 1 300 C. It is a further object of this invention to provide an integral compacted base-metal thermocouple cable and sensor which are highly oxidation resistant up to 1 300 C.

It is another object of the invention to provide electrically conductive cables and heating elements which have similar advantages at high temperatures.

It is a further object of this invention to provide electrically conductive cables and heat detectors which have similar advantages at high temperatures.

These and other objects of this invention are achieved, in one aspect of the invention, by the use of two specific alloys, and certain compositional variants of these alloys, as sheath materials.

The said alloys are similar to those which are suitable for use as the positive and negative thermoelements of the thermocouple. The chemical compositional tolerances (percentages by weight) for the alloying constituents of the alloys for the positive and negative thermoelements of the thermocouple conductors are- Positive Alloy Element Negative Alloy 14.2 + 0.15 ----------- Cr ------------- 0.02 max.

1.4 + 0.05 ----------- Si ------------- 4.4 + 0.2 0.1 + 0.03 ----------- Fe ------------- 0.1 + 0.03 0.03 max. ----------- C -------------- 0.03 max.

Mg ------------- 0.1 + 0.05 Balance ----------- Ni ------------- Balance Thermocouples of these alloys are designated 'type N' by the Instrument Society of America and other such bodies.

iron, about 0.05 percent weight maximum of carbon, and the balance nickel.

A specific preferred composition of type (a) consists essentially, within the usual limits of manufacturing tolerance of: (a3) 14.2 weight percent chromium, 1.4 weight percent silicon, 0.1 weight percent iron, 0.03 weight percent magnesium and the balance nickel.

Preferred compositions of type (b) consist essentially of: (b1) from about 4.0 weight percent to about 4.8 weight percent of silicon, from about 0.05 weight percent to about 0.20 weight percent of magnesium, and the balance nickel, or more preferably: (b2) from about 4.2 percent weight to about 4.6 percent weight silicon, from about 0.10 weight percent to about 0.20 weight percent magnesium, about 0.05 weight percent maximum chromium, about 0.1 5 weight percent maximum iron, about 0.05 percent weight maximum of carbon, and the balance nickel.

A specific preferred composition of type (b) consists essentially, within the usual limits of manufacturing tolerance of: (b3) 4.4 weight percent silicon, 0.1 weight percent iron, 0.1 weight percent magnesium and the balance nickel It will be clearly understood that when the cable contains a single thermoelement, the most preferred sheath material is the thermoelectrically opposite alloy to the said single thermoelement. In this case a sensor is formed by joining the thermoelement to the sheath. When more than one thermoelement is employed and the thermoelements are made of dissimilar alloys, the sheath material is most preferably made of the same alloy as any one of the thermoelements.

In a further modification of the invention, of particular value in hostile environments such as are encountered in the chemical and petroleum industries, the sheath may be fabricated of appropriate corrosion resistant material.

The invention will be further illustrated by the following non-limiting examples.

EXAMPLE 1 The integral compacted thermocouple cable of this Example is fabricated using existing manufacturing procedures. They begin with thermoelectrically matched thermoelement wires surrounded by non-compacted ceramic insulating material held within a metal tube. By rolling, drawing, swaging, or other mechanical reduction processes the tube is reduced in diameter and the insulation is compacted around the wires. The manufacturing process parameters are adjusted so that the ratios of sheath diameter to wire-size and sheath wall-thickness offer a balance between maximum wall-thickness and suitable insulation spacing for effective insulation resistance at elevated temperatures.

An important feature of the fabrication process is that considerable attention is given to the initial cleanliness and chemical purity of the components and retention of a high degree of cleanliness and dryness throughout fabrication. As already noted above, to make an actual sensor from this cable, the cable is cut and the ends of the conductors are exposed by removing some of the insulation therefrom. The exposed ends of the conductors are then joined to form a thermojunction, which may be accomplished for example by crimping and/or welding.

The thermojunction may simply be left exposed for use in appropriate environments, or may be protected by capping the sheath over the thermojunction with or without insulant. The measuring thermojunction of the thermocouple is usually, but not always, electrically isolated from the end of the sheath.

In this example, the alloys for the thermocouple conductor wires are those specified above as type N and the alloy for the sheath is that specified in (a) above.

An important feature of the finished product of this example is that the essential similarity between the properties of the sheath alloy and the thermocouple conductor alloys virtually eliminates the destructive influences of thermocouple contamination by cross-diffusion, mechanical failure due to differential thermal stresses, and accelerated oxidation above about 1 050 C.

The strains caused by longitudinal stresses arising during thermal cycling are small because of the very small differences in the temperature coefficients of lineal expansion between the materials of the sheath and of the thermoelement conductors. Some typical average values of these coefficients of expansion are: Component Material x 10-6'C-' (1200"C) sheath alloy (a) above 1 7.5 thermoalloys type N 17.0 (average of positive and negative) EXAMPLE 2 The integral compacted thermocouple cable and sensor of this Example is the same as described in Example 1, except that the alloy for the sheath is that specified (awl) above used in lieu of that alloy specified (a) above.

EXAMPLE 3 The integral compacted thermocouple cable and sensor of this Example is the same as described in Example 1, except that the alloy for the sheath is that specified (a2) above used in lieu of that alloy specified (a) above.

EXAMPLE 4 An integral compacted thermocouple cable is made as in Example 1, the composition of the components being: positive thermoelement - alloy (a3) negative thermoelement - alloy (b3) sheath - alloy (a3) EXAMPLES 5 to 8 The thermocouple cables of these Examples are the same, respectively, as those described in Examples 1 to 4 except that the sheath alloys are strengthened by addition of one or more components known for the purpose of increasing mechanical strength of said alloys at high temperature for example one or more of manganese, iron, molybdenum, cobalt, tungsten, and oxide-particle dispersions.

EXAMPLES 9 to 16 The integral compacted thermocouple cables and sensors of these Examples are the same, respectively, as those described in Examples 1 to 8, except that the sheath alloys are coated to further inhibit chemical high-temperature corrosive degradation. Such coatings include those deposited by a wide variety of conventional protective coating processes such as electrolytic deposition from aqueous solution or fused salts or other electrolytic liquids, such as metallic diffusion processes including aluminizing, chromizing, calorizing and similar processes, such as overlay coatings, and other protective coating processes.

EXAMPLE 17 The integral compacted thermocouple cable and sensor this Example is the same as described in Example 1, except that the alloy for the sheath is that specified (b) above used in lieu of that alloy specified (a) above.

EXAMPLE 18 The integral compacted thermocouple cable and sensor of this Example is the same as described in Example 1, except that the alloy for the sheath is that specified (b1) above used in lieu of that alloy specified (a) above.

EXAMPLE 19 The integral compacted thermocouple cable and sensor of this Example is the same as described in Example 1, except that the alloy for the sheath is that specified (b2) above used in lieu of that alloy specified (a) above.

EXAMPLE 20 The integral compacted thermocouple cable of this example is the same as Example 4 except that the sheath is composed of alloy (b3) instead of alloy (a3).

EXAMPLES 21 to 24 The integral compacted thermocouple cables and sensors of these Examples are the same, respectively, as those described in Examples 1 7 to 20 except that the sheath alloys contain in addition up to 1.0 weight percent of one or more elements known for the purpose of inhibiting metailurgical grain growth, occurring at high temperature, for example niobium or titanium.

EXAMPLES 25 to 28 The integral compacted thermocouple cables and sensors of these Examples are the same, respectively, as those described in Examples 1 7 to 20, except that the sheath alloys contain in addition an appropriate amount of one or more components known for the purpose of increasing mechanical strength of said alloys at high temperature, for example manganese, iron, molybdenum, cobalt, tungsten, and oxide-particle dispersions.

EXAMPLES 29 to 32 The integral compacted thermocouple cables and sensors of these Examples are the same as those described, respectively, in Examples 1 7 to 20, except that the sheath alloys contain in addition up to 1.0 weight percent of one or more elements known for the purpose of inhibiting metallurgical grain growth occurring at high temperature, for example niobium or titanium; and also an appropriate amount of one or more components known for the purpose of increasing mechanical strength of said alloys at high temperature, for example manganese, iron, molybdenum, cobalt, tungsten, and oxide-particle dispersions.

EXAMPLES 33 to 48 The integral compacted thermocouple cables and sensors of these Examples are the same, respectively, as those described in Examples 1 7 through 32, except that the sheath alloys are coated by any of the processes and for the purposes described in Example 9 through Example 16.

EXAMPLES 49 to 96 Heat detectors in accordance with the invention are produced in the same manner as the integral compacted cables of examples 1 through 48 except that the refractory compacted insulant incorporates insulating properties with a high negative temperature coefficient of resistance.

EXAMPLES 97 to 576 Heating elements in accordance with the invention are produced in the same manner as the integral compacted cables of examples 1 through 96, except that a single resistive heating conductor is used in each case and the said conductor is composed of an alloy which is respectively: positive type N, (a), (a1), (a2) or (a3).

It will be clearly understood that the invention in its general aspects is not limited to the specific details referred to hereinabove.

Claims

1. A compacted mineral-insulated integrally sheathed cable, characterised in that the cable includes at least one thermoelement composed of a type N alloy, and the sheath is composed of an alloy having similar characteristics to the alloy of which the or at least one thermoelement is composed.

2. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of a positive N-type alloy.

3. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of a negative N-type alloy.

4. A cable according to claim 1 characterized in that the cable includes one only thermoelement, said thermoelement is composed of a positive N-type alloy and the sheath is composed of a negative N-type alloy.

5. A cable according to claim 1 characterised in that the cable contains one only thermoelement, said thermoelement is composed of a negative N-type alloy and the sheath is composed of a positive N-type alloy.

6. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy chosen from the group consisting of (a) and (b) in which (a) consists essentially of from about 13.0 weight percent to about 15.0 weight percent of chromium, from about 1.0 weight percent to about 2.0 weight percent of silicon, from about 0.03 weight percent to about 0.25 weight percent of magnesium, and the balance nickel; and (b) consists essentially of from about 3.0 weight percent to about 5.0 weight percent of silicon, from about 0.03 weight percent to about 0.25 weight percent of magnesium and the balance nickel.

7. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy (al) consisting essentially of from about 13.9 weight percent to about 14.5 weight percent of chromium, from about 1.3 weight percent to about 1.5 weight percent of silicon, from about 0.05 weight percent to about 0.20 weight percent of magnesium, and the balance nickel.

8. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy (a2) consisting essentially of from about 14.05 percent weight to about 14.35 percent weight of chromium, from about 1.35 percent weight to about 1.45 percent weight of silicon, from about 0.10 weight percent to about 0.20 weight percent of magnesium, about 0.15 percent weight maximum of iron, about 0.05 percent weight maximum of carbon, and the balance nickel.

9. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy (a3) consisting essentially of 14.2 weight percent chromium, 1.4 weight percent silicon, 0.03 weight percent magnesium and the balance nickel.

10. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy (b1) consisting essentially of from about 4.0 weight percent to about 4.8 weight percent of silicon, from about 0.05 weight percent to about 0.20 weight percent of magnesium, and the balance nickel.

11. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy (b2) consisting essentially of from about 4.2 percent weight to about 4.6 percent weight silicon, from about 0.10 weight percent to about 0.20 weight percent magnesium, about 0.05 weight percent maximum chromium, about 0.1 5 weight percent maximum iron, about 0.05 percent weight maximum of carbon, and the balance nickel.

1 2. A cable according to claim 1 characterised in that the cable includes a thermoelement composed of a positive N-type alloy and a thermoelement composed of a negative N-type alloy and the sheath is composed of an alloy (b3) consisting essentially of 4.4 weight percent silicon, 0.1 weight percent iron, 0.1 weight percent magnesium and the balance nickel.

1 3. A cable according to claim 1 characterised in that the cable includes one only thermoelement, said thermoelement is composed of a positive N-type alloy and the sheath is composed of an alloy selected from the group consisting of (b), (b1), (b2) and (b3) respectively consisting of: (b) from about 3.0 weight percent to about 5.0 weight percent of silicon, from about 0.03 weight percent to about 0.25 weight percent of magnesium and the balance nickel; (b1) from about 4.0 weight percent to about 4.8 weight percent of silicon, from about 0.05 weight percent to about 0.20 weight percent of magnesium, and the balance nickel; (b2) from about 4.2 percent weight to about 4.6 percent weight silicon, from about 0.10 weight percent to about 0.20 weight percent magnesium, about 0.05 weight percent maximum chromium, about 0.15 weight percent maximum iron, about 0.05 percent weight maximum of carbon, and the balance nickel; (b3) 4.4 weight percent silicon, 0.1 weight percent iron, 0.1 weight percent magnesium and the balance nickel.

14. A cable according to claim 1 characterised in that the cable contains only one thermoelement, said thermoelement is composed of a negative N-type alloy and the sheath is composed of an alloy selected from the group consisting of (a), (a1), (a2) and (a3) respectively consisting essentially of: (a) from about 13.0 weight percent to about

15.0 weight percent of chromium, from about 1.0 weight percent to about 2.0 weight percent of silicon, from about 0.03 weight percent to about 0.25 weight percent of magnesium, and the balance nickel; (a1) from about 13.9 weight percent to about 14.5 weight percent of chromium, from about 1.3 weight percent to about 1.5 weight percent of silicon, from about 0.05 weight percent to about 0.20 weight percent of magnesium, and the balance nickel;; (a2) from about 14.05 percent weight to about 14.35 percent weight of chromium, from about 1.35 percent weight to about 1.45 percent weight of silicon, from about 0.1 0 weight percent to about 0.20 weight percent of magnesium, about 0.15 percent weight maximum of iron, about 0.05 percent weight maximum of carbon, and the balance nickel; (a3) 14.2 weight percent chromium, 1.4 weight percent silicon, 0.03 weight percent magnesium and the balance nickel.

1 5. A resistive heating element particularly useful for operation at high temperatures comprising a cable according to claim 1 containing one or more thermoelements and a sheath, characterized in that the thermoelements and the sheath are composed of alloys which may be the same or different, and said alloys are chosen from the group consisting of positive N-type alloys, negative N-type alloys, and alloys (a), (awl), (a2), (a3), (b), (b1), (b2) and (b3) as defined in claims 1 3 and 14.

16. A compacted mineral-insulated integrally sheathed thermocouple cable, characterised in that the cable includes at least one thermoelement composed of a type N alloy, and the sheath is composed of a type N alloy, further characterised in that the alloy of which the sheath is composed is thermoelectrically opposite to the alloy of which the or at least one thermoelement is composed.

1 7. A heat detector operable at temperatures above about 1100 C comprising an elongated compacted mineral insulated integrally sheathed cable as defined in claim 16, disposed in an environment where local rises in temperature may occur, causing local increase in the conductivity of the insulating material, said detector including means for determining the location of the said local increase in conductivity and hence the location of the said rise in temperature.

1 8. A stagnation temperature probe incorporating a type N thermocouple as the temperature sensor, said thermocouple being made from a cable as defined in claim 1.

1 9. A cable according to any one of claims 1 to 18, in which the sheath alloy is strengthened by addition of one or more components known for the purpose of increasing mechanical strength of said alloys at high temperature.

20. A cable according to claim 19, in which the said components are chosen from the group consisting of manganese, iron, molybdenum, cobalt, tungsten, and oxide-particle dispersions.

21. A cable according to any one of claims 1 to 18, in which the sheath alloy contains in addition one or more elements known for the purpose of inhibiting metallurgical grain growth occurring at high temperature.

22. A cable according to claim 21 in which the said elements are chosen from the group consisting of niobium and titanium.

23. A cable according to any one of claims 1 to 1 8 in which the sheath alloy contains in addition one or more components known for the purpose of increasing mechanical strength of said alloys at high temperature, and one or more elements known for the purpose of inhibiting metallurgical grain growth occurring at high temperature.

24. A cable according to claim 23, in which the said components are chosen from the group consisting of manganese, iron, molybdenum, cobalt, tungsten, and oxide-particle dispersions, and the said elements are chosen from the group consisting of niobium and titanium.

25. A compacted mineral-insulated integrally sheathed cable substantially as hereinbefore described with reference to any one of the foregoing examples.