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Thermoelectric hysteresis in nickel-based thermocouple alloys

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1989 J. Phys. D: Appl. Phys. 22 1902

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J. Phys. D: Appl. Phys. 22 (1989) 1902-1907. Printed in the UK

Robin E Bentley
CSlRO Division of Applied Physics, Lindfield, Australia 2070

Received 21 March 1989, in final form 22 June 1989

Abstract. Hysteresis in the Seebeck coefficient has been studied for type K and
type N thermocouples. The temperature range was 0 to 1200 "C, heating periods
were up to 530 h and the alloys were supplied from a number of different sources
(five for type K and two for type N). In both types, changes of about 1% in
Seebeck coefficient were found but the hysteresis extended over a larger
temperature range for the type N thermocouple. Thermoelectric hysteresis is a
major cause of instability in Ni-based thermocouples, especially in the more stable,
Nicrosil-sheathed mineral-insulated configuration. It is shown that it is possible to
produce type K thermocouples with a performance comparable with that previously
reported for type N.

1. Introduction and the letter designation 'type K' does not specify a
particular composition but simply its EMF-temperature
The thermoelectricinstability in Ni-based mineral-insu- relationship.Therefore,astudy of Nicrosil-sheathed
latedmetal-sheathed(MIMS)thermocouples is due type K probesshouldincludetype K materialfrom
mainly to reversible changes in the Seebeck coefficient, different sources.
especially below 900 "C [ 1,2]. Such changes, giving rise In this study, samples of type K material from five
to hysteresis in the signal, have been reported earlier differentsourcesandsamples of typeNfrom two
forthetypeN alloys.Nicrosil and Nisil, in astudy sources were compared at temperatures up to 1200 "C.
which involved heating periods of up to 300 h and tem- All thermoelements were within
Nicrosil-sheathed
peraturesfrom 0 to 1200 "C[2].Abroad hysteresis MIMS probes. To ensure that any differences observed
peakextendingto 1000 "C was found ineach alloy were due to the starting alloys, and not to the method
which amounted to a 1% change in the Seebeck coef- of manufacture of MIMS cable, all probeswerepro-
ficient for the thermocouple. duced by .an identicalprocess. The effect of manu-
Data on reversiblechanges in thetype K ther- facturing variables on the thermoelectric properties of
mocouplealloys, Chromelt and Alumelt, are incom- Nicrosil-sheathed probes will be the subject of a later
plete.Hysteresis in Chrome1hasbeenstudiedupto study.
600 "C [3,4] for heating periods from 0.7 to 720 h, and
in both alloys upto 550 "C,butonlyforaheating
period of 15 h [ 5 ] . 2. Specimens
The use of the MIMS configuration for
ther-
mocouplesavoidsthe relativelylargeeffects of oxi- Thirty-seven specimen probes were used, each being a
dation on theSeebeckcoefficient,seen in bare-wire 1 mlongNicrosil-sheathed ' M I M S thermocouple with
thermocouples, and the use of a Nicrosil sheath avoids high-purity (>99.5%) MgOinsulation.Theoutside
the effect of Mn [2]. Mn is present in the conventional diameter of each sheath was 1.5, 3 or 6 mm and its
sheathing alloys Inconel+and stainless steel,and chemicalcomposition was 84Ni 14.2Cr1.5Si0.15Mg
migrates readily to the thermoelements causing insta- O.1Fe (values are in weight %). The measuring junc-
bility in the Seebeck coefficient. Thus reversible tionortip of eachthermocouple was welded to its
changes in the coefficient are more significant in Nicr- sheath.
osil-sheathedprobesandmoredataarerequiredfor The specimens were cut fromMIMS coils sufficiently
the type K alloys before the design of such probes can far from the ends to avoid end effects (swaging etc)
be optimised. Furthermore, hysteresis depends on the and all coils wereproduced by PyrotenaxAustralia
chemical composition and the physical state of an alloy, using the same precautions against contamination and
moisture,thesamediesequenceand with the same
t Registered trademarks of Hoskins Manufacturing Co. anneals. Each coil was drawn down from an assembly
$ Registered trademark of the INCO group of companies in which the two 1.83 mmdiameterthermoelement

0022-37271891121902 + 06 $02.50 @ 1989 IOP Publishing Ltd

 Thermoelectric hysteresis

Table 1. Chemical composition of thermoelements, in weight per cent, with the remainder being Ni.

Source Mn
Cr Si AI C
CO Mg
cu Fe

Positive thermoelements
K1 9.1 0.45 0.00 0.02 0.00 0.00 0.40 0.00 0.05
0.30 9.7 K2 0.01 0.02 0.00 0.00 0.1 5 0.00 0.03
0.42 9.1 K3 0.00 0.01 0.02 0.00 0.27 0.00 0.01
9.5 K4 0.47 0.00 0.01 0.03 0.00 0.42 0.00 0.01
9.1 K5 0.40 0.00 0.02 0.04 0.01 0.37 0.07 0.01
N1 13.9 1.56 0.05 0.02 0.01 0.01 0.12 0.08 0.08
N2 14.0 1.42 0.00 0.03 0.01 0.00 0.07 0.03 0.03
Negative thermoelements
K1 0.00 1.88 1.62 1.28 0.56 0.00 0.12 0.00 0.06
K2 0.00 1.95 0.36 0.02 0.37 0.00 0.07 0.00 0.10
K3 0.00 2.15 0.01 0.02 0.96 2.22 0.21 0.00 0.02
K4 0.01 1.64 1.78 1.56 0.56 0.00 0.04 0.00 0.03
K5 0.01 1.59 1.76 1.67 0.53 0.02 0.09 0.08 0.03
N1 0.00 4.35 0.01 0.00 0.00 0.00 0.17 0.07 0.16
N2 0.00 4.30 0.00 0.00 0.00 0.00 0.16 0.08 0.01

rodswerefrom
Threehadtype
one of sevensources(seetable
K formulations with aMn-andAl-
bearing Alumel: K1 was air smelted, K4 was vacuum
1).
100 l
smelted and K5 was given an atypicaldrawing treat-
ment. The K5 rods were produced with a diameter of
4.5 mm and then reduced to 1.83 mm by a different
company, in planta used for
drawing
resistance
(heater) wires. The degree of cold work, the annealing
andtheprecautionsagainstcontamination may not
have been appropriate for thermocouple grade alloys;
for example, the presence of Mg is atypical (table 1). I
The other type K formulations, K2 and K3, had no AI
and little Mn. O I I
Type N material from two sources was included for
comparison purposes. Itwas also useful for interpreting -
theresults, sincetype
positionalsimilarities

N1 alloys, thedatapresented
study [2].
N alloyshave
with thetype
some com-
K alloys. No
measurements were made on samples containing the
beingfrom anearlier

Compositionaldata in table 1 wereobtained by

-
l

titrimetric analysis for Cr, gravimetric analysis for Si,

ahigh-temperaturecombustiontechniqueforCand
atomic absorption spectroscopy for the other elements.
3. Experimental method
3.1. Gradient-anneal/scanningfacility
MIMS specimens were heated for various times, to, and
theresultantchange in theSeebeck coefficient, SS,
was determined as a continuousfunction of immersion
depth, x , for each thermoelement. Each was heated
in aknown temperature profile T o ( x ) . Thus SS was
obtained as a continuous function of To for various to
from 1 to 530 h.
Theapparatusand its method of usehavebeen
describedearlier [2]. Briefly,specimenswereheated
L
0
Immersion [mm 1
Figure l . Temperature profiles in the gradient-annealing
furnace (top) and the scanning furnace (bottom) shown
relative to a MIMS specimen. The relationship between a
particular 7''and x is shown as an example.
in a 'gradient-annealing' furnace, having a known tem-
perature profile (see figure l ) , and thermoelectrically
scannedbeforeandafter by drivinga steeptem-
peraturestepalongtheirlength.Thermoelectric sig-
natures wereproducedforeachthermoelement(see
figure 2) as a plot of ( E - Erer)against position. E is
the output of the thermoelement relative to Pt, for the

1903
 R E Bentley

1 " " " " ' l Thus, a 'recovery anneal'was selected and routinely
applied as a means of determining the reversible com-
ponent of any change, 6s. The recovery anneal con-
sisted of immersing a probe in a uniform-temperature
furnace at a temperature near1030 "C and withdrawing
it 5 min after it reached 1000 "C. The withdrawal took
about 2 S and the probe was then held stationary in air
at 20 "C till cool. Typically, for a 3 mm diameter probe
quenched in this way, the sheath temperaturefell from
1000 to 500 "C in 25 S and from 500 to 300 "C in the
0 500 1000
same time.
lmmerslol ( m m 1
Because of non-linearity in the temperature profile,
the gradient-annealing furnace was limited in its range
500
l I
400
1 a

300 200
I II
of use: for example, to about 350"C, for a peak tem-
To ['Cl perature of 1000°C. So the study was broken up into
Figure 2. Thermoelectric signatures for Chrome1 ( K l ) number
a of annealing/scanning sequences.
Each
relative to Pt: after recovery anneals (---) and after an sequence began with a fresh set of specimens, usually
intermediate 16 h heating in the gradient-annealing furnace three in number,one of eachdiameter (1.5, 3 and
(-1. 6mm), and covered the same temperature range. The
sequences had peak annealing temperaturesof 500,800
or -1050 "C and were arranged as follows:
interval -20 to -500 "C, and Erefis the corresponding (i) recovery anneal,
value from the reference tables [6,7]. (ii) scan,
Expressing E as a function of S we have (iii) recovery anneal to reverse changes caused by

E= 1
T=20
500 dT
S(x,T) -dx.
dx
scan,
(iv) gradient anneal for a period to,
(v) scan,
Hence the difference, 6 E , between signatures (figure (vi) recovery anneal,
2) received before and after a gradient anneal is (vii) scan,

6E = 1
T=20
500
6S(T,
To,
to)dT (1)
(viii) repeat steps (iii) to (vii) for a different to.
The reversiblechangesproduced by agradient
anneal in the 4th step of the sequence are obtained
where the initial inhomogeneity of the material, i.e., by subtracting,fromthesignature of step(v),that
its inherent dependence on x, tends to cancel and can interpolated from the signatures of steps (ii) and (vii).
be ignored. Of course, 6S still varies with x through The values of to were typically in the following
TO. order:16, 1, 500, 64, 200 and 16 h. By repeating
If 6S is assumedindependent of T,equation (1) measurements for to = 16 h in this way, any tendency
reduces to for hysteresis to be reduced by the progressive effect
of heat treating the alloys near 1000 "C (the recovery
6S(To, t o )= 6€/480. (2)
anneals)couldbedetected.Insomecases,an iso-
All values of 6S giveninthis paper were calculated thermal heat treatment for 2 h at 1100 "C was applied
using this expression; the repeatability of the scanning near the end of an anneal/scan sequence to examine
facility on the same specimen is such that changes in the effect of this more severe treatment.
signature of 5 pV (0.01 pV K-') or more are significant.
Whether 6S(To, to) is independent of Tuptoat
least T = To, as assumed above, is examined elsewhere 4. Results and discussion
[8]. Inparticulartemperature regions ( T o ) andfor
some alloys 6S varies with T, in which case calculations The reversible changes in the Seebeck coefficient for
of behaviour based on the dataof this paper would not the various positive and negative thermoelements are
be simple functions of &S [8]. given in figures 3 and 4. The figures show the depen-
dence of reversible change on annealing temperature
foraheatingperiod of 200 h.Thenet effectwhen
3.2. Measurement of reversible change
thermoelementsarecombinedasthermocouples is
Preliminary measurements [2] revealed that no signifi- given in figure 5 . The data in figures 3, 4 and 5 apply
cant reversible changes occur in type K or type
N alloys to all sheath diameters: no significant dependence on
above1000°Candthatwhen suchchangesoccurat diameter was found. Reversible effects in the N1 [2]
lower temperatures, heating the alloys for a few min- and K1 alloys were studied for all three diameters, 1.5,
utes at temperatures above 1000 "C reverses the pro- 3 and 6 mm, and for the others only for 1.5 and 3 mm
cess. Such behaviour is repeatable. sheaths.

1904
 Thermoelectric hysteresis

9
O l n

-0.21 ' I I I
I
i
J
0 5 00 1000 To ('C)
To ('C) Figure 5. Net reversible change in the Seebeck coefficient,
Figure 3. Reversible change in the Seebeck coefficient, 6S,for type K and type N thermocouples heated for 200 h
6S, of the positive thermoelements, Chromel (K1 to K5) at temperature To (calculated from figures 3 and 4). Also
and Nicrosil (N1 and N2), for 200 h of heating at indicated is the percentage change in coefficient: -
temperature To:-K1, K4; -.- K5; ---- K2, K3; K1, K4; - * - K5; ---- K2, K3; N1, N2.
.... N1, N2.

terms of Pollock's spin-cluster model [l21 is difficult to

accept because the model describes the dependence of
S on T rather than on t .
L In contrast,theextent of hysteresis in Nicrosil
dependsmoreonthesource of the alloy (micro-
structure, minor constituents etc) than on its nominal
composition. The two Nicrosils,
having
hysteresis
peaks at similar temperatures, have peak heights dif-
fering by two to one. I suggest that the carbide Cr&
may formreversibly in Nicrosil at intermediate tem-
peratures,around
700"C,
and dissociate above
1000 "C. Itsformation wouldreducethe Cr content
and thus increase S by 0.8 pV K" for each per cent of
- 0 4 / ~ ~ Cr (for Ni ~ 14Cr [13]).
~ To account
~ for the~major hys- ~ ~
0 500 1000
teresis peak in N1 (figure 3) a reduction of 0.4% Cr
TO incl needstobeassumed, which corresponds to only
Figure 4. Reversible change in the Seebeck coefficient, 0.024% in C. Theeffect of a similar quantity of carbide
SS, of the negative thermoelements, Alumel (K1 to K5) and in Chromel would be small because S goes through a
Nisi1 (N1 and N2), for 200 h of heating at temperature
To: -K1, K4; -.- K5; ---- K2, K3; N1, N2.
S . * .
maximum around Ni 9Cr and so is insensitive to small
changes in the Cr content.
Hysteresis in each of the negative thermoelements
(figure 4) is similar in that each has two peaks, near 350
Clearly,hysteresis in theChromels(figure 3) is and 600°C. However,themagnitude of thepeaks
distinctly different from that in the Nicrosils: the for- varies considerably; from zero for the K2 Alumel to
mer have a single peak near 400 "C and the latter have -0.25 pV K" for N1. The peaks for N2 and for the
two peaks, the major one being at about 700°C. twoMn-andAl-bearingAlumels,K1 andK4,were
6S in each of the Chromels, with the exception of intermediate in height, being -0.1 pV K-l.
K4 (the only alloy vacuum smelted) is the same. For The correlation between the composition of nega-
K4, the peak temperature is different from that of the tive thermoelements (table 1) and hysteresis (figure 4)
others but the area underits curve is similar. Thus, the is poor. So the reversiblechanges in Seebeckcoef-
contribution from reversible change toin situ drift (see ficientforthese alloys are possibly dueto physical
below) is about the same for all Chromels. The simi- characteristics, such as the microstructure, or to phases
larity in the curves for Chromel from different sources (Ni and Si) and/or intermetallic compound formation
is consistent with earlier suggestions that hysteresis in with trace elements. This suggestion is consistent with
-
Ni 10Cr is a direct consequence of having -10% Cr the effects of heat treatment described below.
and, in particular, that it is likely due to short range The height and temperature of each hysteresis peak
ordering of theNiCrlattice[9,10].Thealternative change with heating time, to. The height, I 6SPk( , pro-
suggestion[l11 that hysteresismaybeexplained in gressively increases with time, as seen in figure 6, and

1905
R E Bentley
I , ( 1 , 0 1 ,
0.1 1 10 100
to (h)
Figure 6. Height of each hysteresis peak, SS,,, for type K
and type N thermocouples as a function of heating time, to.
The approximate TDkfor each set is shown, in "C.
*ool
Figure 7. Peak temperature, Tpk,for the major hysteresis
regions of type K and type N thermocouples as a function
of heating time, to.
thepeaktemperaturedecreases(figure7). Inboth
cases the change is linear in log to, over the three dec-
ades considered. This is consistent with earlierwork
on Chromel by Fenton [3,4]. His data, when plotted
against log to for the four decades from 0.07 to 720 h,
are also linear. It is reasonable to assume then that this
relationship extends at least one decade, to lo4h say.
Earlier work by Burley et a1 [7] indicating that hys-
teresis in thetypeNthermocouple is two orders of
magnitude less than in type K, should be reconsidered
in the context of figure 6. Their data were obtained for
aheatingperiod of -1 handwererestrictedtothe
alloys Nicrosil and Chromel and to temperaturesbelow
-500 "C. They are therefore consistent with figure 6,
for Tpk= 350 "C and to = 1 h. However, because of
changes in Nisil the position is different at larger to.
For the thermocouple N1, because of its greater slope
1906
( T p k = 350 "C), hysteresis is a third of that in the type
K thermocouple at to= 16 h and increases to a similar
level at -lo4 h. In contrast, the peak for N2 remains
roughly four times smaller for to > 10 h.
On the other hand, the height of the one peak for
eachtype K thermocouple(near 400°C; figure 5 ) is
intermediate in value compared with the higher-tem-
perature peaks for the two type N thermocouples and
remains so for all to (figure 6).
The hysteresis phenomenadescribedaboveare
repeatable.Forexample,duringthe annealing/scan-
ning sequences (0 3.1) the responses to thetwo anneals
with to = 16 h, one at each endof each sequence, were
the same. Moreover, tenrecovery anneals did not dim-
inish the effect, i.e. heating for up to 1 h at -1010 "C
8 1 , ' had no noticeable effect on hysteresis.
1000 However, the more severe heat treatment of 2 h at
1100 "C did have a significant effect. The earlier study
of N1 alloys [2] showed that suchheating,applied
before a 16 h gradient anneal, reduced the high-tem-
peraturepeak in Nicrosil by anaverage of -20%
(3 mm sheath), with the reduction having an inverse
dependence on diameter. It was also found that both
peaks in Nisil were reduced by an average of -50%
and again thereduction was greaterforthe smaller
diameters. A 2 h isothermal heat treatment at 1100 "C
was applied to theK4 alloys before and after a gradient
anneal for to = 64 h. It reduced the peak in Chromel
by an average of 20% with an inverse diameter depen-
dence. The low-temperature peak in Alumel was hal-
ved, as with Nisil, but the high-temperature peak was
unaffected.
The K3 Alumel was heat treated for 2 h at 1100 "C
because of its unusually large peak near 600 "C (figure
4). The heat treatment had a greater effect than noted
with the other alloys;iteliminatedhysteresis in the
two specimens studied. They had diameters of 1.5 and
3 mm and 6 s p k reduced to SO.01 pV K-'. Another
unusual feature of high-temperature hysteresis in this
alloy is that it has poor sample-to-sample repeatability.
The peak given in figure 4 is the largest one found
(3 mm sheath).
The EMF of a thermocouple used for a long period
of time, with its tiptemperature held constant, will
drift. The in situ drift occurs because at each point, at
thetemperature To within thetemperaturegradient
region, the Seebeckcoefficient changes. Thus, the drift
in signal is
AE = lo
T
6 S ( T o )d T o (3)
where the cold junction temperature was taken as0 "C,
for convenience.
Thus by integrating under the curves of figure 5 ,
the component of A E arising from reversible changes
in the Seebeck coefficient was obtained and is shown
in figure 8 for all seven alloy combinations.Inter-
estingly, the thermocouple combination with the great-
est reversible component is the type N pair, N1, and

1 5 0 9
t ,'
/""""I
~-7""-
T ('Cl
Figure 8. Calculated contribution from reversible changes
in the Seebeck coefficient to the in situ drift, AE, of as-
received (quenched) Ni-based thermocouples with tips held
at temperature T for 200 h. An approximate equivalent
temperature change is also shown: -K1, K4; - * -
K5; ---- K2, K3; N1, N2.
* e * .
that with the least is N2. Intermediate in behaviour are
the two type K thermocouples, K1 and K4.
However, care must be taken when interpreting the
significance of A E . The assumption was made in using
equation (3) that 6S(To,T ) is independent of T up to
at least T = To (see 0 3.1). For the contributions from
Chromel and Nicrosil, this is not true; 6S is a constant
from T = 0 to a value near To, where it dcreases [8].
Long-term drift measurements on probes with K1 and
N1thermoelements suggest thatthe reversiblecon-
tribution to high-temperature in situ drift is -70% of
A E [8].
5. Conclusion
There is one significant hysteresis peak in the Seebeck
coefficient foreach of the positive thermoelements,
Chromel and Nicrosil, but it occurs at different tem-
peratures: at 400 "C for Chromel and700 "C for Nicro-
si1.
The change in the Seebeck coefficient for each of
the seven negative thermoelements is similar, in that
each has two hysteresis peaks at 350 and 600 "C. How-
ever, the changes in the Mn- and Al-bearing Alumels,
K1 and K4, are less than in the Nisils and they would
contribute
little
to
high-temperature in situ drift
(>700 "C) in a type K thermocouple because its two
peaks have similar areas and are of opposite sign.
The overall effect of reversible change in the two
thermocoupletypes, K and N, is similar.Forboth
Thermoelectric hysteresis
types, major peaks of about 1% in S occur and hys-
teresis contributes about 2 "C to long-term drift at high
temperatures. On the other hand there are signfiicant
differences:
(i) Hysteresis in thetype K thermocouplepre-
dominates at a lower temperature than it does in type
N, -400 "C for K rather than -700 "C for N.
(ii) Hysteresis in the type K thermocouple extends
over a smaller temperature range: 200-600°C for the
Mn- and Al-bearing type K alloys, for example, com-
pared with 200-1000 "C for the type N.
Acknowledgment
The author is grateful to Pyrotenax Australia for sup-
porting the project financially and for providing all the
MIMS specimens.
References
[ l ] Bentley R E and Morgan T L 1986 Ni-based
thermocouples in the mineral-insulated metal-
sheathed format: thermoelectric instabilities to
1100 "C J . Phys. E: Sci. Instrum. 19 262-8
[2] Bentley R E 1987 Thermoelectric hystereis in Nicrosil
and Nisil J . Phys. E: Sci. Instrum. 20 1368-73
[3] Fenton A W 1969 Errors in thermoelectric
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[4] Fenton A W 1972 The travelling gradient approach to
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[S] Bentley R E 1983 Short-term instabilities in
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[l31 Bentley R E 1988 Theory and practice of
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1907