LMEC-Memo-68-10

Limited Distribution

liquid M e t a l Temperature Measurement

(Sodium)
State-of -the-Art-Study

J.S. Hochheiser

Liquid M e t a l Engineering Center

Operated for
the U.S. Atomic Energy Commission by Atomics International
A Division of North American Rockwell Corporation

w Contract: AT( 04-3)-700

Issued: M a y 31, 1968

DtSTRlBUTlON OF fKci 00CUMW 6 UNLlMIl&
 DISCLAIMER

This report was prepared as an account of work sponsored by an

agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.
 DISCLAIMER

Portions of this document may be illegible in

electronic image products. Images are produced
from the best available original document.
n
 CONTENTS

Page
Abstract .......................................... 7
I. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
I1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
III. Behavior of M a t e r i a l s with T e m p e r a t u r e . . . . . . . . . . . . . . . . . 15
A . General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
B . Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
C . Mechanical P r o p e r t i e s . . . . . . . . . . . . . . . . . . . . . . . . . . 17
D. Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
E . Chemical P r o p e r t i e s . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1. Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2 . Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3 . Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4 . Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
F . Electrical Properties........................... 22
1. Conductivity (Resistivity) . . . . . . . . . . . . . . . . . . . . . . 22
2 . Thermionic E m i s s i o n . . . . . . . . . . . . . . . . . . . . . . . . 24
IV . Reference Standards and Calibration . . . . . . . . . . . . . . . . . . . 27
A . National B u r e a u r of Standards (NBS) Accuracy of
Realization of t h e Thermodynamic T e m p e r a t u r e Scale ..... 27
B . P r a c t i c a l T e m p e r a t u r e Scales Employed by NBS for the
Calibration of T e m p e r a t u r e - M e a s u r i n g Instruments ....... 27
C . NBS Photometric Standards ....................... 30
D . Calibration of T e m p e r a t u r e - M e a s u r e m e n t I n s t r u m e n t s ..... 32
V . T e m p e r a t u r e M e a s u r e m e n t Techniques and I n s t r u m e n t s ....... 37
A . T he r m o e l e ct r ic The r m o m e t r y . . . . . . . . . . . . . . . . . . . . . 37
1. Thermoelectricity . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2 . Advantages and Limitations of Thermocouples . . . . . . . . 38
3 . M e a s u r e m e n t and Calibration ................... 39
4 . Thermocouple F a b r i c a t i o n . . . . . . . . . . . . . . . . . . . . . 44
5 . Thermocouple Installation . . . . . . . . . . . . . . . . . . . . . 45
6 . Thermocouple M a t e r i a l s . . . . . . . . . . . . . . . . . . . . . . 48

LMEC-Memo-68- 10
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 CONTENTS

Page
B . Resistance T h e r m o m e t r y ........................ 52
1 . Metals .................................. 54
2. Semiconductors ............................ 54
H o t - w i r e Techniques . . . . . . . . . . . . . . . . . . . . . . . . .
3. 57
Thin Metallic L a y e r s . . . . . . . . . . . . . . . . . . . . . . . .
4. 57
5 . Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

C . Radiation P y r o m e t r y . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
1 . Optical .................................. 59
2 . .......................
E mi s sion Spe c t r o s copy 62
3 . I n f r a r e d Photography . . . . . . . . . . . . . . . . . . . . . . . . . 63
D . T h e r m a l Expansion of M a t e r i a l s . . . . . . . . . . . . . . . . . . . 64
1. Liquid T h e r m o m e t e r s . . . . . . . . . . . . . . . . . . . . . . . . 64
2 . Gas T h e r m o m e t r y . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3 . Bimetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4. Filled System Thermometers . . . . . . . . . . . . . . . . . . . 67
E . Variations in Dielectric Constants . . . . . . . . . . . . . . . . . . . 67
F . Thermionic E m i s s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
G . Acoustic .................................... 69
1. Velocity of Sound i n Gas . . . . . . . . . . . . . . . . . . . . . . . 69
2 . Frequency-Change . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3 . P ha s e -Relation ............................. 70
4 . S p a r k Gap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
H. T h e r m o c h e m i c a l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
I. Fixed Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
J. Phosphor Luminescence ......................... 72
K. Noise Generated i n E l e c t r i c a l E l e m e n t s . . . . . . . . . . . . . . . 72
L . Diffusion . . . . . . . . . ........................... 73
.
M Pneumatic Apparatus ........................... 75
N. P y r o m e t r i c Cones T a p e s and P a i n t s . . . . . . . . . . . . . . . . . 75
1. P y r o m e t r i c Cones ........................... 75
2 . T a p e s and P a i n t s ........................... 76

LMEC -Memo-68 .10

4
 CONTENTS

Page
0. ...............................
Pyroelectricity 76
P. Microwave Resonant Cavities . . . . . . . . . . . . . . . . . . . . . 76
VI. Effects of Liquid Metal R e a c t o r Environments o n
T e m p e r a t u r e M e a s u r e m e n t Instruments ................. 79
A. Radiation Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
B. Radiation Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
C. Differential Compton C i r c u i t s . . . . . . . . . . . . . . . . . . . . . 80
D . Ionization Chamber Effects . . . . . . . . . . . . . . . . . . . . . . . 80
E. T h e r m i o n i c E m i s s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
F. W a t e r c y c l e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
G. E l e c t r o s t a t i c Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
H. Chemical Effects .............................. 82
I. Vibration ................................... 82
VII. L i t e r a t u r e Survey ................................ 83
A. Thermocouple Development for P r o j e c t Rover, 2500°C . . . . 83
B. High T e m p e r a t u r e T h e r m o m e t r y . . . . . . . . . . . . . . . . . . . 83
C. .....................
Fast Response T h e r m o c o u p l e . 85
D. Fuel-Pin Temperature Measurement . . . . . . . . . . . . . . . . 85
E. Thermocouple Stability and Reliability i n Liquid Metal . . . . . 85
F. Thermocouple Development for a Lithium-Cooled R e a c t o r . .. 85
G. T h e Effect of P r e s s u r e on T e m p e r a t u r e C a l i b r a t i o n . ...... 85
H. G r a d i e n t Approach t o Thermocouple C i r c u i t r y . .......... 86

References ........................................ 87

Appendix .......................................... 91

TABLE

1. T h e r m o e l e c t r i c S e r i e s of Selected Metals and Alloys .......... 49

LMEC-Memo-68-10
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 FIGURES

Page
1. Relative Melting P o i n t s of Some E l e m e n t s , Oxides, and
Carbons. ....................................... 18
2. Melting Points of Metals, Alloys, and C e r a m i c s ............. 19
3. Soldering, Brazing, and Welding P r o c e s s e s . . . . . . . . . . . . . . . . 20
4. E l e c t r i c a l Resistivity of R e f r a c t o r y Oxides ................ 25
5. E l e c t r i c a l R e s i s t a n c e of Sintered Alumina ................. 25
6. Accuracy of Realization of the Thermodynamic T e m p e r a t u r e
Scale. ......................................... 28
7. Calibration of T e m p e r a t u r e - M e a s u r i n g I n s t r u m e n t s . . . . . . . . . . . 29
8. ........
P r e c i s i o n and Accuracy of NBS P h o t o m e t r i c Standards. 31

9. Representative Ice-Bath Calibration F i x t u r e . . . . . . . . . . . . . . . . 33

10. Cross-Section of F r e e z i n g Point Standard C e l l (Aluminum). . . . . . 33
11. F u r n a c e Used in Calibrating Thermocouples a t F r e e z i n g
Points of Metals .................................. 34

12. Schematic of Drift T e s t F a c i l i t y . ....................... 35

13. Typical Ice Bath f o r Reference Junctions . . . . . . . . . . . . . . . . . . 42

14. Differential Thermocouple BAB and M e t e r M M e a s u r e the

.........................
T e m p e r a t u r e Difference t3 -tl 43

15. N Thermocouples i n S e r i e s Acting a s a T h e r m o p i l e . . . . . . . . . . . 43

16. N Thermocouples i n Parallel Providing a M e a s u r e m e n t of

the T e m p e r a t u r e Mean Among t l , t 2 . . t
n
. ................. 43

17. Single Thermocouple - Double-Bore C e r a m i c Insulators ....... 46

18. Single Thermocouple - Fish-Spine C e r a m i c Insulators . . . . . . . . . 46
19. Double Thermocouple - F o u r - H o l e C e r a m i c I n s u l a t o r s . ........ 46
20. Exposed Loop Thermocouple . . . . . . . . . . . . . . . . . . . . . . . . . . 46
21. Gasket T h e r m o c o u p l e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
22. Mixture Thermocouple . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
23. Shielded T h e r m o c o u p l e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
24. Sheathed Thermocouple . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
25. T h e r m o E l e c t r i c Go., Inc., Patented P i p e Clamp Adapter . . . . . . 47
26. Boron Graphite/Graphite Thermocouple, Coaxial Style. ........ 48
27. R e s i s t a n c e - T e m p e r a t u r e C h a r a c t e r i s t i c s of Some M a t e r i a l s . . . . . 53
28. Advanced Thermocouple Concepts . . . . . . . . . . . . . . . . . . . . . . 54

LMEC-Memo-68-10
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 ABSTRACT

A study of the available techniques and devices f o r making

t e m p e r a t u r e m e a s u r e m e n t s applicable to liquid m e t a l (sodium)
nuclear power r e a c t o r s i s presented. Included in t h i s study i s
a review of the calibration and standards a c c u r a c i e s available,
a study of the behavior of m a t t e r with t e m p e r a t u r e and with
e x p o s u r e t o liquid m e t a l r e a c t o r environments, a n d a l i t e r a t u r e
s u r v e y a s an aid to those who r e q u i r e details beyond the scope
of this document. The Appendix c a r r i e s a review of t h e funda-
mentals of t e m p e r a t u r e and t e m p e r a t u r e m e a s u r e m e n t theory
plus a l i s t of definitions.

LMEC-Memo-68-10
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n
 I. SUMMARY

By f a r the majority of t e m p e r a t u r e m e a s u r e m e n t s i n liquid sodium r e a c t o r s

a r e made with thermocouples. At the e x t r e m e high end, e. g . , 1000 to 5 0 0 0 " F ,
tungsten/ rhenium thermocouples provide the highest sensitivity with good s t a -
bility. Combinations of W5Re/W26Re and W3Re/W25Re a r e p r e f e r a b l e because
of t h e i r b e t t e r initial low t e m p e r a t u r e ductility than that of unalloyed tungsten.
An advantage i n using W5Re/W26Re is the availability of a ductile, compensated
leadwire that matches the emf vs t e m p e r a t u r e c h a r a c t e r i s t i c s f r o m 32 to 1200°F
within *O. 11 mv.

T h e choice of e l e c t r i c a l insulations n a r r o w s down to B e 0 and T h o Z . B e 0

p e r f o r m s v e r y well up t o its melting t e m p e r a t u r e of about 4 5 0 0 ° F . T h o 2 has
a substantially higher melting t e m p e r a t u r e , 5972°F; however, i t s e l e c t r i c a l
r e s i s t a n c e d e c r e a s e s a s the t e m p e r a t u r e approaches 4000°F and will r e s u l t i n
an 8% reduction in emf at 5011°F. The shunting effect of the d e c r e a s e d r e s i s -
tance above 4 2 0 0 ° F can be c o r r e c t e d f o r i n the calibration of the thermocouple.
P e r f o r m a n c e is reproducible and insensitive t o thoria impurities and to im-
mer sion depth.

W26Re is a n alloy c o m m e r c i a l l y available i n the f o r m of tubing used f o r

sheathing. T e s t s indicate it i s compatible with P u 0 2 - U 0 2 f u e l at t e m p e r a t u r e s
up to 2700°F f o r t i m e s i n e x c e s s of 500 h r . At t e m p e r a t u r e s i n the vicinity of
5000"F, however, the lifetime m a y be limited t o s e v e r a l h o u r s .

Chromel/Alumel thermocouples, insulated with MgO and sheathed with

Inconel (0.012-in. -diameter w i r e , 0.062-in. OD x 0.009-in. w a l l ) , a r e used
for m e a s u r i n g coolant t e m p e r a t u r e s . Such thermocouples will respond with a
t i m e constant of less than 0.1 s e c .

The effect of neutron transmutation on tungsten/rhenium and C h r o m e l /

Alumel thermocouple signals is s m a l l but detectable.

B a r e w i r e thermcouples (0.010-in. w i r e s ) will have response times of

100 m s o r b e t t e r . Sheathed thermocouples will have response t i m e s in the
o r d e r of seconds, depending on s i z e and construction. In measuring fuel, the
response t i m e is strongly influenced by the heat t r a n s f e r coefficient between
fugl and thermocouple, which may change substantially a s t h e fuel c r a c k s and

LMEC-Memo-68- 10
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s i n t e r s and f o r m s c e n t r a l voids in-pile. Although s m a l l e r d i a m e t e r t h e r m o -
couple a s s e m b l i e s will exhibit f a s t e r r e s p o n s e t i m e s , those with a l a r g e r
d i a m e t e r will give b e t t e r life expectancy.

"Viewing" high t e m p e r a t u r e with optical m e a s u r e m e n t techniques h a s many

advantages w h e r e the visibility m a k e s this technique applicable. Optical p y r o m -
e t e r s a r e , i n fact, the s t a n d a r d f o r t e m p e r a t u r e s above 2 0 0 0 ° F . Infrared
photography h a s provided l a r g e a r e a and t e m p e r a t u r e gradient m e a s u r e m e n t
a t a glance i n a single reading.

P l a t i n u m w i r e r e s i s t a n c e t h e r m o m e t r y provides the highest a c c u r a c y and

repeatability up to about 1200°F. The disadvantages a r e physical s i z e and t h e
f a c t that it i s not a point s e n s o r .

Other novel m e a s u r i n g techniques and devices have been explored, such a s

acoustic and microwave, to solve peculiar t e m p e r a t u r e m e a s u r e m e n t p r o b l e m s .
Probably the m o s t significant goal i s a r r i v i n g at a means f o r making r e l i a b l e ,
long t e r m ( y e a r s ) m e a s u r e m e n t s w i t h a device not subject t o d e t e r i o r a t i o n f r o m
the hostile a t t a c k s of the high t e m p e r a t u r e liquid sodium and its t r a c e i m p u r i t i e s .

LMEC-Memo-68- 10
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 II. INTRODUCTION

In principle, n e a r l y e v e r y p r o p e r t y of a m a t e r i a l which changes with t e m -

p e r a t u r e in a repeatable, well defined way can s e r v e a s a t e m p e r a t u r e m e a -
suring device. The v a r i e t y of such devices a r e many. It i s the purpose of t h i s
I

r e p o r t to d e s c r i b e a l l the m e a n s that conceivably m a y be employed f o r t e m p e r -

a t u r e m e a s u r e m e n t s i n sodium r e a c t o r power g e n e r a t o r s y s t e m s o r in liquid
sodium t e s t p r o g r a m s . In s o doing, t h i s document provides a f u l l s p e c t r u m of
t e m p e r a t u r e instrumentation, serving a s a p r i m e r f o r those new to the field,
and as a check list f o r t h o s e experienced in the field.

F u r t h e r m o r e , it is not t h e intention of t h i s study to p r e s e n t a "cook book"

of r e c i p e s f o r making t e m p e r a t u r e m e a s u r e m e n t s but r a t h e r to r e p o r t devel-
opments i n t h e state-of-the-art and the rationale behind t h e s e developments.
Bearing t h i s thought in mind, it m u s t b e understood that making r e l i a b l e t e m -
p e r a t u r e m e a s u r e m e n t s f o r a long period of t i m e i n a hostile environment
entails t h e integrated efforts of s e v e r a l disciplines, which encompass: the
behavior of m a t e r i a l s at t e m p e r a t u r e e x t r e m e s ; the effect of radiation o n the
instrumentation; techniques f o r calibration and standardization; the v a r i o u s
t e m p e r a t u r e dependent physical phenomena; and such p r a c t i c a l considerations
a s fabrication and installation. T h i s r e p o r t is divided into sections and sub-
sections which t r e a t each of t h e s e subjects s e p a r a t e l y .

Also, t h e r e h a s been much work done in recent y e a r s covering specific

t e m p e r a t u r e m e a s u r e m e n t problems and t h e i r solutions. The d e t a i l s of t h e s e
s t u d i e s a r e too n u m e r o u s t o repeat h e r e ; t h e r e f o r e , a l i t e r a t u r e survey is
included to d i r e c t the r e a d e r t o f u r t h e r information of significant value. Finally,
a list of r e f e r e n c e s and a n Appendix, which includes s o m e generalized infor-
mation, a r e added as a convenience to the r e a d e r .

SOME PRECAUTIONARY NOTES

Before selecting a method f o r making a t e m p e r a t u r e m e a s u r e m e n t s o m e

words of warning should be kept in mind. It is not enough to simply s e l e c t
and install the proper t e m p e r a t u r e m e a s u r i n g s y s t e m ( s e n s o r , protective
housing o r sheath, read-out i n s t r u m e n t , e t a l . ) i n o r d e r t o d e t e r m i n e the

LMEC -Memo-68- 10
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t e m p e r a t u r e of a p a r t i c u l a r object o r region. T h e r e a r e many ways that the
t r u e t e m p e r a t u r e of the object i n question c a n deviate f r o m the value indicated.
Not the least of these is a consequence of the f a c t that no t e m p e r a t u r e m e a -
suring device c a n do m o r e than r e l a t e the t h e r m a l s t a t e which it itself a t t a i n s .
In other words, the t e m p e r a t u r e differential between the sensitive portion of
the t r a n s d u c e r (e. g . , t h e thermocouple junction) and the object must be mini-
mized. It is not considered good p r a c t i c e , n o r a r e the n e c e s s a r y data usually
available, to c o r r e c t the poor installation by the u s e of computed c o r r e c t i o n
factors. Among the precautions t o be observed, s o m e of which a r e obvious,
a r e those d i s c u s s e d in t h e following p a r a g r a p h s .

When using t h e r m o m e t e r s (as opposed t o p y r o m e t e r s , s e e Definitions i n

the Appendix), provide good t h e r m a l contact between the t h e r m o m e t e r and
the medium being m e a s u r e d . (A colloidal suspension of silver and silicone
g r e a s e has b e e n used to improve t h e r m a l conductivity to the t e m p e r a t u r e s e n s o r . )
However, do not l e t the t h e r m o m e t e r p e r t u r b t h e conditions of the medium. A
heavy-gage thermocouple w i r e o r its thick-walled protection tube may conduct
heat into o r out of a small specimen. For example, i n EBR-I (Mark 111 and IV)
it was n e c e s s a r y t o add a c o r r e c t i o n f a c t o r of t4O"C i n measuring s m a l l d i a m e t e r
f u e l slug t e m p e r a t u r e s a t the center of the r e a c t o r a t full power.

If the t e m p e r a t u r e being m e a s u r e d c a n v a r y rapidly, be s u r e that t h e

response t i m e of the t h e r m o m e t r i c device will allow it to follow the fluctuations.

A thermocouple that has given s e r v i c e over a period of time may a p p e a r to

be i n good condition, but the alloy of one leg may have diffused into the other
leg. This would change the couple m a t e r i a l composition, hence its calibration.

The effectiveness of the e l e c t r i c a l insulation, afforded the w i r e of a t h e r m o -

couple by its protection tube, is a strong function of the t e m p e r a t u r e and the
tube m a t e r i a l . It is r a t h e r s u r p r i s i n g how rapidly some insulators degrade
above t e m p e r a t u r e s of 1000°C. This is a n important factor to be considered
i n t h i s t e m p e r a t u r e region.

While the effect of leadwire r e s i s t a n c e i n thermocouples i s generally

appreciated, the somewhat i n v e r s e effect of s t r a y t h e r m a l e r n f ' s i n r e s i s t a n c e
t h e r m o m e t e r s i s s o m e t i m e s overlooked. The flow of c u r r e n t through the r e -
sistance t h e r m o m e t e r , a n absolute requirement f o r i t s operation, m u s t be
n

LMEC -Memo-68- 10
12
minimized t o avoid self-heating. This type of e r r o r can become appreciable if
the t h e r m o m e t e r i s i m m e r s e d in a medium w h e r e heat t r a n s f e r is poor. An
actual t e s t using different c u r r e n t s i s the simplest way t o d e t e r m i n e the extent
of e r r o r , if any.

A problem s o m e t i m e s overlooked with s t a i n l e s s s t e e l sheathed thermocouples

involves running calibration t e s t s a t t e m p e r a t u r e s above 1 0 0 0 ° F . At t e m p e r a -
t u r e s of 1000 to 1 2 0 0 ° F the s t e e l becomes permanently sensitized to s t r e s s c o r -
rosion by halogens. After the t e s t , chlorine and other halogens p r e s e n t in the
air m a y s t a r t c o r r o s i o n of the thermocouple, which will significantly affect its
life in s e r v i c e .

As a p o s t s c r i p t t o the foregoing, it should be r e a l i z e d t h a t , numerous a s

a r e the methods of t h e r m o m e t r y , t h e r e a r e a l m o s t a s many c r i t e r i a to be
applied in selecting one of these methods for a p a r t i c u l a r application. One m a y
have t o consider a c c u r a c y , stability, sensitivity, reproducibility, speed of
r e s p o n s e , reliability, life, linearity of output, t e m p e r a t u r e range of useability,
e a s e of reading, simplicity, safety, s i z e and weight, adaptability to automatic
recording a n d / o r control, f i r s t cost and maintenance cost, e t c . P e r h a p s in no
other b r a n c h of m e a s u r e m e n t technology i s it so important to “let the u s e r
beware ’.

LMEC-Memo-68- 10
13
 Ill. BEHAVIOR OF MATERIALS WITH T E M P E R A T U R E
c3
A. GENERAL

It i s commonly understood that as t e m p e r a t u r e r i s e s m a t e r i a l s melt, o r

l o s e s o much s t r e n g t h that t h e i r s t r u c t u r a l value diminishes. However, t h e s e
a r e not the only phenomena which affect the utility of m a t e r i a l s . At high t e m -
p e r a t u r e s the cohesive f o r c e s which hold m a t e r i a l s together weaken and mechan-
i c a l as well a s chemical and e l e c t r i c a l stabilities a r e d e c r e a s e d .

The examination of t h r e e typical m a t e r i a l s , tungsten, silicon carbide and

magnesium oxide, will s e r v e to i l l u s t r a t e the m e c h a n i s m s that c a n b e expected
a t elevated t e m p e r a t u r e s .

In silicon carbide, a typical covalent "giant molecule," the cohesive f o r c e s

a r e v e r y strong a t o r d i n a r y t e m p e r a t u r e s . At 300°K the probability i s only
that a molecule will have enough energy t o b r e a k one of its four e l e c t r o n -
p a i r bonds between a t o m s . At 3000°K t h i s probability i n c r e a s e s to t h e o r d e r
of At about 2100°C S i c begins t o undergo a phase t r a n s i t i o n f r o m the
cubic beta to the hexagonal alpha f o r m . At 2400°C (4350°F) it decomposes.
Similarly, the v e r y h a r d diamond f o r m of carbon undergoes a phase transition
to graphite at 1600 to 1900°C. The i n c r e a s e d energy of the molecules m a k e s
it relatively e a s y to have enough e n e r g y concentrated i n one band to b r e a k it;
t h e r e f o r e , s t r u c t u r e s which a r e stable a t lower t e m p e r a t u r e s do not endure a t
the s e higher t e m p e r a t u r e s .

Magnesium oxide is a n ionic c r y s t a l , and e l e c t r o s t a t i c f o r c e s hold it t o -

gether. As a r e s u l t of t h e r m a l expansion, the a v e r a g e distance between ions
grows and the cohesive f o r c e s become weaker. More important, the disruptive
f o r c e s due t o t h e r m a l motion and vibration of t h e ions i n c r e a s e greatly. Crys-
tals r e a r r a n g e into m o r e stable and less deformed s t a t e s (sintering). F r e e
electrons and holes become m o r e common, and the e l e c t r i c a l resistivity d r o p s
continuously with rising t e m p e r a t u r e . Deformation of the c r y s t a l s becomes
e a s i e r and a l m o s t all the mechanical s t r e n g t h is lost. T h e r m a l conductivity
r e m a i n s low, s o that the t h e r m a l shock p r o p e r t i e s of the m a t e r i a l a r e poor.
Eventually (at 2200°C) the vapor p r e s s u r e becomes appreciable; since the
vapor is composed of MgO molecules, t h i s indicates a breakdown of the ionic
crystal structure. The melting point is 2620°C ( 4 7 5 0 ° F ) .

LMEC-Memo-68-10
15
 The mechanical phenomena i n tungsten a r e m o r e complex than i n magnesium n

oxide, but the b a s i c principle h e r e too is the r e a r r a n g e m e n t of molecules t o

m o r e stable f o r m s . Powder metallurgy techniques r e l y on c r y s t a l growth,
o c c u r r i n g well below the melting point, f o r the t r a n s f o r m a t i o n of tungsten
powder t o b a r tungsten. Actual tungsten m a t e r i a l s , such as b a r s and w i r e s ,
have been swaged and drawn a f t e r annealing, and the c r y s t a l s have been broken
up. Hence, exposure of tungsten w i r e , f o r example, t o t e m p e r a t u r e s of the
o r d e r of 25OO0C, c a u s e s extensive recrystallization. Grain boundaries, which
w e r e previously aligned p a r a l l e l with the axis of the w i r e a s a r e s u l t of the
drawing operation, now c a n be found running i n a t r a n s v e r s e direction; the
s t r e n g t h of t h e w i r e ( s o exceptional before heating) i s greatly reduced. After
cooling, the frozen-in g r a i n boundaries c a u s e g r e a t b r i t t l e n e s s . Non-sag
w i r e s have been perfected, i n which a n additive r e t a r d s o r d i r e c t s the g r a i n
growth. In addition to mechanical t r a n s f o r m a t i o n , the chemical reactivity of
tungsten is greatly i n c r e a s e d at high t e m p e r a t u r e s . Reaction with oxygen i s
instantaneous and violent. Tungsten w i l l also r e a c t w i t h c a r b o n at tempera-
t u r e s m o r e than 1000°C below i t s melting point. It is unstable i n the presence
of w a t e r vapor, molten oxidizing s a l t s and other oxidizing media.

F r o m t h i s p r e l i m i n a r y s u r v e y it i s s e e n that a l l specifications m u s t be
g r e a t l y relaxed a t high t e m p e r a t u r e s . In building t e m p e r a t u r e m e a s u r i n g
devices designed to o p e r a t e inside a n u c l e a r r e a c t o r , e x t r e m e values of tensile
strength, e l e c t r i c a l resistivity, chemical i n e r t n e s s , e t c . , a r e not to be expected.

Since it i s not the purpose of t h i s study to r e p e a t i n detail m a t e r i a l which

is adequately covered in o t h e r documentation, the r e a d e r is d i r e c t e d t o Vol. I11
of Reference 1 f o r f u r t h e r information o n the mechanical, t h e r m a l , e l e c t r i c a l
and chemical p r o p e r t i e s of m a t e r i a l s a t high t e m p e r a t u r e . However, some of
the m o r e salient generalizations a r e included in the following text.

B. ALLOYS

Alloys of m e t a l s typically have melting t e m p e r a t u r e s somewhat below

those of each of the element m e t a l s alone. The eutectic of a n alloy i s the
point of maximum fusibility, o r the combination r a t i o of the element m e t a l s
which f o r m s t h e lowest melting point alloy.

LMEC-Memo-68-10
16
 - . . . .. . ..

C. MECHANICAL PROPERTIES
@ P e r h a p s the m o s t striking of mechanical p r o p e r t i e s i s c r e e p : the change
of dimensions under s t r e s s due to r e c r y s t a l l i z a t i o n and annealing phenomena.
C r e e p i s relatively low f o r tungsten. Molybdenum shows c r e e p r a t e s up to
l % / h r under 12,500 p s i at 2,000"F.

Zirconia b e c o m e s p l a s t i c above 1300°C. Many m a t e r i a l s which have been

subjected t o high t e m p e r a t u r e s a r e b r i t t l e at r o o m t e m p e r a t u r e .

D. THERMAL PROPERTIES

The t h e r m a l conductivity of m e t a l s does not change a p p r e c i a b l y with t e m -

perature. The t h e r m a l conductivity of oxides generally d e c r e a s e s with elevated
t e m p e r a t u r e s ; MgO and A1203 d e c r e a s e about a n o r d e r of magnitude f r o m 0 to
1500°C. Z r O Z (stabilized) however, i n c r e a s e s its t h e r m a l conductivity slightly
with t e m p e r a t u r e . F i g u r e s 1, 2, and 3 provide a handy r e f e r e n c e of s o m e of
the t h e r m a l p r o p e r t i e s of some commonly used m a t e r i a l s .

E. CHEMICAL PROPERTIES

Since the m o r e complicated molecules d i s s o c i a t e at c o m p a r a t i v e l y low

t e m p e r a t u r e s , only the relatively simple compounds survive at v e r y high t e m -
peratures. T h e chemical reactions which need to be taken into consideration
a r e a l s o few; e s s e n t i a l l y t h e s e a r e combinations of the elements with oxygen,
nitrogen, hydrogen, and c a r b o n . The c o n v e r s e r e a c t i o n s of dissociation of
oxides, n i t r i d e s , hydrides, and c a r b i d e s a r e a l s o of c o n c e r n , a s a r e the solution
p r o c e s s of one m e t a l into another and the f o r m a t i o n of a e u t e c t i c .

1. Oxygen

Carbon, molybdenum, tungsten, tantalum, rhenium, and a l l c a r b i d e s and

n i t r i d e s will r e a c t with oxygen at elevated t e m p e r a t u r e . The r a t e of oxidation
depends on the n a t u r e of the oxide. If the oxide f o r m s a c o h e r e n t l a y e r o v e r
the s u r f a c e of the m a t e r i a l , the r a t e - d e t e r m i n i n g s t e p is diffusion of oxygen
through the oxide l a y e r , and the amount of oxide f o r m e d will be proportional
to t h e s q u a r e root of the t i m e .If the oxide is volatile (Moo3, W O ) o r f o r m s
3
a discontinuous l a y e r ( e . g . , if its volume i s s m a l l e r than t h a t of t h e unoxidized
m a t e r i a l f r o m which it i s f o r m e d ) , the oxygen always h a s a c c e s s to t h e m e t a l
s u r f a c e and the amount of oxide f o r m e d is proportional to the t i m e .

LMEC-Memo-68- 10
17
 ELEMENTS OXIDES CARBIDES

---
4000 - 4TaC:lHfC (3942)
-- I-
4TaC:lZrC (3932)
- HfC (3887) --
- TaC (3877)
--
-
-- C CARBON* (3652)
(6600" F)
--
ZrC (3530)
3500- NbC (3500) -
---W TUNGSTEN (3410)
Ta2 C (3400) --
- Tho2 (3300) -
- -
- -
--

-
-
-
--Ta TANTALUM (3027)
TIC (3140)
-
3000 - --
- MgO (2800) wc (2867)
--
- W2C(P) (2857)
-
- vc (2830) --
Os OSMIUM (2700) Zr02 (2677) (2692) --
----Mo MOLYBDENUM (2625) Ce02 ,CaO (2600)
(2 68 7)
-
- Be0 (2550)
(2655)

---
2500 ThC (2625)
-- IR IRIDIUM (2454)
--Nb NIOBIUM (2415) SrO (2415) S
'C
I* (2600)
--- (2450) -

- -
B BORON (2300)
-
- Cr203 (2265) uc2 (2350) --
uc (2250) -
0 - T1203 (2130) Be2C' (2100) --
e --Hf HAFNIUM (2110)
c

W - A1203 (2015)
$ 2000 --Rh RHODIUM
!x
(1996) V203 (1977) / "3'2 (1890) --
d
W
n
---H-Zr C r CHROMIUM
ZIRCONIUM
(1890)
(1830) U2C3+ (1800) -
-
z --Pt Th THORIUM (1827) Cr7C3 (1665) -
W
F - PLATINUM (1774) -
VANADIUM
-<V T i TITANIUM (1735) Fe3 C (1650) -
- (1725) Cr23C6 (1550) --
- Pd PALLADIUM (1549)
Mn3C - (1520)
Fe IRON (1535)
1500
-\Co COBALT (1495) -
- NI NICKEL (1455)
(1400) --
--\ S I SILICON (1420)
--
--Be BERYLLIUM (1278)
- -
- -
- -
-T A CuU COPPER (1083)
CUO (1026) -
GOLD (1063)
ol oo- Ag SILVER (961) -
-7
Ge GERMANIUM (959) -
Ba BARIUM -
--Ca
- CALCIUM
(850)
(842)
-
-
-Sr
- STRONTIUM (757)
(660)
--
--AI Mg ALUMINUM --
- MAGNESIUM
-c S b ANTIMONY
(651)
(63 1)
As ARSENIC* (615)
500--Te TELLURIUM (452) -
--Zn -
-
ZINC (419)
--
-
Pb LEAD
-<Cd Bi CADMIUM
(327)
(32 1) -
- BISMUTH
-k S S ne TIN
(271)
(232) +DECOMPOSES
--
SELENIUM (217) -
-
- -
0
5-2-68 7694-55206

Figure 1. Relative Melting Points of Some Elements,

Oxides, and Carbons

LMEC -Memo- 68 10 -
18
 TEMPERATURE
ALLOYS
CERAMICS OF OC METALS

7000 4000
THORIA (Th 02) I GRAPHITE
-TUNGSTEN
CALCIA (Ca 0 ) TANTALUM
BERYLLIA (Be O)--I I MO L Y BDEN U M
COL UM BI U M
STRONTIA Sr 0
-
BARIA Ba 0
I
3500,4
3400
L

3300 =i 1800
1900 ZIRCONIUM

THORIUM
- T I TAN IU M
3200 - -
- PLATINUM
QUARTZ S i 0 2 3100rL
1700
3000-
-- CHROMIUM
2900 -
- 1 1600 PALLADIUM
DURALOY 18-8
KOVAR
NICHROME I V
,1 2800-
2700 - l5O0
IRON

NICKEL
INCONEL 1’ 2600~ri
2500- -
1400
TOPHET A
- BERY L L l U M

NICKEL COINAGE, PRE-WAR USA

2400Ei-
2300
2200 - - 1200
l3O0

PLATINUM SOLDER
2100 - :
2000 =- 1100 COPPER
GOLD
Au 37.5, Cu 6 2 . 5
BRASS Cu 85, 15 Zn 1
1800 SILVER
BARIUM
Au 80, Cu 20
CALCIUM
1500 STRONTIUM
BT
1400
- -
1300 -- 700
EASY-FL03 1 - ALUMINUM
EASY-FLO 45 -7
1200 --
- MAGNESIUM 1
1100 -- 6 0 0
GOLD 80, INDIUM 20 -
1000- -
9 0 0 = 1 500
Sn 60, Ag 40 -
ZINC
8oori - 400
700-- MERCURY (BOILS)
6oo - - LEAD
30-70 SOFT SOLDER
-500 -
50-50 SOFT SOLDER - TIN
400 --- 200
63-37 SOFT SOLDER I 300 - INDIUM
- -
200 -- l o o
5-2-68 7694-55207
F i g u r e 2. Melting Points of Metals, Alloys, and C e r a m i c s

LMEC -Memo- 68 - 10
19
 ALLOYS FOR SOLDERING AND BRAZING
TEMP OPERATION FLUX TEMP COMPONENTS REMARKS NAME
/
OF OC

240

220 -1200
WELDING <

2001
-

OF OC
180(
-1000 ,
800--98 2

{
HIGH-
EMPERATURE DRY BORAX
- BRAZING
5 4 Cu, 4 6 Zn
160( 600--871 SPELTER
PASTE BRAZING
10 BORAX+ ALLOY
BORIC ACID 50 Ag, 34 Cu, GENERAL
- 800 +WATER
4 2 5--7 74
PURPOSE ETX
140( 45 Ag, 30 Cu,
j l L V E R SOLDER
HA N DY FL UX 340-- 7 2 7
5 A g , 5 0 Cu,5 Pb ONLY S I L FOS
300-- 704 NON-FERROUS

120c EASY - F LO
1 7 5 - - 635 PURPOSE:
100--593 IRON, STAIN-
- 600 LESS STEEL,
BRASS,
1000

800 INTERMEDIATE
(a) SOLDER
- 400 PASTE
75 0-L3 9 9
90
PETROLATUM
600 1 0 NH4 CI
(h) i4 5 - - 2 8 5
RESIN I N
i A L F AND H A L F
ALCOHOL I64-- 2 4 0
(C)
400 -200 63 Sn, 37 Pb FREEZES EUTECTIC
40 Z n Cl2, 3 6 1-- 183 AND M E L T S
2 0 NH4CI, A T SAME

1
40 H 2 0
(d)
200 RESIN 50 Bi 13 C d WOOD'S M E T A L
.42 61
2 5 Ph 1 2 Sn
100
5-2-68 7694-55208

Figure 3 . Soldering, Brazing, and Welding P r o c e s s e s

LMEC-Memo - 68 - 1 0
20
 T h e r e is a l s o a volume -diffusion mechanism which l e a d s t o formation of
metallic i n t e r s t i t i a l suboxides s u c h a s Mo 0.
3
2. Nitrogen

The formation of n i t r i d e s is due to the solid solution of nitrogen a t o m s .

Two p r o c e s s e s a r e t h e r e f o r e necessary: t h e catalyzed dissociation of nitrogen
at the s u r f a c e ,

1/2N2 = N ,
and t h e diffusion of a t o m s f r o m one i n t e r s t i t i a l position t o another, deeper one.
The f o r m e r may be expected to go t o a n equilibrium, s o that the concentration
of nitrogen a t o m s is expected to be proportional t o the s q u a r e . r o o t of the p a r t i a l
p r e s s u r e of nitrogen. The r a t e of the l a t t e r p r o c e s s i s governed b y a n activation
-4
energy. At 2500"K, t h e activation energy f a c t o r s e -E'RT v a r y f r o m 1.2 x 10
f o r beta titanium t o 1.1 x f o r thorium. Allowing f o r l o l o - 1013 effective
vibrations per second, it can be s e e n that the t r a n s p o r t r a t e of N a t o m s will be
rapid and will approach a s t r a i g h t diffusion p r o c e s s .

The n i t r i d e s of T i , Z r , Hf, Th, V, Nb, and T a a r e stable up t o high t e m -

peratures. The n i t r i d e s of molybdenum and tungsten, on the other hand, do not
appear to b e stable at high t e m p e r a t u r e s .

3. Hydrogen

The activation e n e r g i e s for the diffusion of hydrogen through t r a n s i t i o n

group m e t a l s a r e v e r y low. Hydride formation should t h e r e f o r e occur e a s i l y
at higher t e m p e r a t u r e s . Hydrides a r e v e r y b r i t t l e and c a n b e pulverized easily.

Metal oxides a r e hydrogen sensitive, and rough calculations indicate that

MgO and B e 0 will have v e r y appreciable dissociation p r e s s u r e s of metal vapor
and HZO gas i n the p r e s e n c e of 1 to 2 0 a t m of hydrogen at 2000 t o 2500°K.

4. Carbon

R a t e s of carburization a r e not known. It is stated, however, that c a r b u r i -

zation of Mo and W is slow i n the solid phase at t e m p e r a t u r e s under 2700°C.
Tantalum c a n be c a r b u r i z e d in relatively thin l a y e r s . Most m e t a l s f o r m single
eutectics with t h e i r c a r b i d e s .

LMEC -Memo -68- 10

21
 Obviously, the preceding information i s only a v e r y brief introduction t o
t h e c h e m i s t r y of m a t e r i a l s at high t e m p e r a t u r e s , with special attention t o
p r o p e r t i e s of solids, and those reactions which might lead to f a i l u r e of s t r u c -
t u r a l elements of a t e m p e r a t u r e probe.

F. ELECTRICAL PROPERTIES

1. Conductivity (Resistivity)

A s h o r t way t o d e s c r i b e the dependence of conductivity on t e m p e r a t u r e is

as follows: f o r metallic sub s t a n c e s , the conductivity d r o p s with t e m p e r a t u r e ,
but not by many o r d e r s of magnitude; f o r semi-conductors and i n s u l a t o r s , the
conductivity r i s e s much f a s t e r , and eventually a l l insulating p r o p e r t i e s b r e a k
down.

The rising r e s i s t a n c e in m e t a l s i s due t o i n c r e a s e d interaction of e l e c t r o n s

with the l a t t i c e of positive ions, a s the l a t t e r is increasingly disturbed by t h e r -
mal motion. The m e a n f r e e path of the e l e c t r o n drops, and s o d o e s its mobility.

In non-metals, t h e r e a r e only a v e r y few electrons i n the conduction bands.

Promotion of electrons to these bands r e q u i r e s a n activation energy. There-
f o r e , the e n t r y of e l e c t r o n s into t h e s e bands r e q u i r e s a n activation energy E ,
and the e x p r e s s i o n f o r the number of conduction e l e c t r o n s includes a t e r m
-E/RT
e .
Thus, when the t e m p e r a t u r e r i s e s , the number of conduction e l e c -
t r o n s i n c r e a s e s rapidly, and i n s o m e t e m p e r a t u r e range t h e r e will be a r a t h e r
s h a r p d r o p in the r e s i s t a n c e . When E is relatively low ( S i c , Z r 0 2 ) , the d r o p
will come i n the moderate t e m p e r a t u r e range. Such substances c a n b e used
as r e s i s t o r s i n e l e c t r i c f u r n a c e s i f preheated to a t e m p e r a t u r e a t which they
a r e no longer good i n s u l a t o r s . Other m a t e r i a l s (MgO) have high E and do not
b r e a k down completely even a t much higher t e m p e r a t u r e s .

Because of chemical and other s u r f a c e s p r o c e s s e s , much of the i n c r e a s e d

conductivity of substances like MgO a t high t e m p e r a t u r e s is s u r f a c e conductivity.
T h e r e f o r e , conductivity tends t o i n c r e a s e with increasing porosity.

Impurities c a n a l s o g r e a t l y i n c r e a s e conductivity. T h e r e a r e at l e a s t two

mechanisms f o r this. F i r s t , impurity a t o m s may f u r n i s h e x c e s s e l e c t r o n s to
t h e conducting bands. In t h i s way, v e r y s m a l l amounts of impurities may
greatly lower the r e s i s t a n c e . Second, s m a l l amounts of i m p u r i t i e s may f o r m

LMEC -Memo-68- 10
22
 __

a s u r f a c e electrolytic zone if they r e a c t chemically with the s u b s t r a t e . This

effect c a n be seen if a n acid oxide, such as S i 0 2 , is added t o a b a s i c oxide,
such a s MgO.

Since many high t e m p e r a t u r e m a t e r i a l s contain impurities, s o m e t i m e s

added deliberately t o improve mechanical p r o p e r t i e s , r e p o r t e d conductivities
( o r r e s i s t i v i t i e s ) v a r y greatly. F o r m e t a l s , s o m e values a r e :

("C) (p-ohm-cm)

Tung st e n 20 5.5
1200 40
240 0 85
3240 118

Molybdenum 20 5.1
1200 33
2000 60
2620 81

Tantalum 20 15
1130 61
1730 80

Platinum 0 11
1600 63

T iN
- 20 21.7
2950 340

7
ZrN 20 13.6
2980 160

Ta2N 20 135
1480 104
2840 116

20 80
w2c
7

2000 125

LMEC-Memo-68 - 10
23
 A g e n e r a l r u l e of thumb is t h a t e l e c t r i c a l r e s i s t i v i t i e s of metallic sub-
s t a n c e s tend t o approach values around 200 x ohm-cm at high t e m p e r a t u r e s . @
The r e s i s t i v i t i e s of oxides a r e shown as a function of t e m p e r a t u r e i n
F i g u r e 4. F i g u r e 5 shows the effect of sintering on high t e m p e r a t u r e r e s i s t a n c e
of alumina. High-sintered m a t e r i a l s , with l e s s s u r f a c e a r e a , a r e s e e n t o have
b e t t e r insulating p r o p e r t i e s . Note t h e inconsistencies in F i g u r e 4, probably due
t o varying amounts of impurities a s well a s different h i s t o r i e s of the m a t e r i a l
samples. Note a l s o that in F i g u r e 5 log R is l i n e a r with 1 / T , in line with the
activation ene rgy concept .
2. Thermionic E m i s s i o n

Thermionic e m i s s i o n i s another e l e c t r i c a l p r o p e r t y which m u s t b e given

attention at high t e m p e r a t u r e s . The thermionic e m i s s i o n of carbides i s l e s s
than that of the element metal. Some r e p r e s e n t a t i v e examples a r e tabulated
a s follows:

Temperature Current
Material
( O K ) (ma/crn2)

Tung s t e n 1800 0.045

Tung s t e n 2200 13.3
Tung s t e n 2600 716.0
Tung s t e n 3000 14,200 .O
Tung s t e n 3200 47,800.0
Tantalum 2000 19.5
TaC 2000 0.32
Molybdenum 1900 1 .o
Tho2 2000 11.0
ThC2 2000 4 .O

LMEC-Memo-68 -10
24
 1oI8 I I I I I I I 1 I
I

i
W
106
t
x
lo4
lo2
loo I
1 I I I I I I I I I I 1
0 2 4 6 8 10 1 2 14 16 18 20 22 24
TEMPERATURE (OC x lo2)
5-2-68 7694-55209
F i g u r e 4. E l e c t r i c a l Resistivity of Refractory Oxides

TEMPERATURE (OC1

4\
"0.53 0.65 0.77 0.89
K x lo3
i / O~

5-2-68 7694-55210
F i g u r e 5. E l e c t r i c a l R e s i s t a n c e of Sintered Alumina

LMEC-Memo- 68- 10
25
 IV. REFERENCE STANDARDS AND CALIBRATION

A. NATIONAL BUREAU OF STANDARDS (NBS) ACCURACY OF REALIZATION

OF THE THERMODYNAMIC TEMPERATURE SCALE

While the Thermodynamic Kelvin Scale (TKS) is completely defined by

assigning a value to the triple-point of w a t e r , this does not b y itself enable one
to r e a l i z e the Scale at any other t e m p e r a t u r e . Using thermodynamic relations,
however, the Scale is r e a l i z e d in different t e m p e r a t u r e ranges using the b e s t
available technique in e a c h range. The Scale is put to p r a c t i c a l u s e b y d e t e r -
mining the Kelvin t e m p e r a t u r e s of a p p r o p r i a t e fixed points (freezing points,
boiling points, etc.). Determinations a r e a l s o made, between the fixed points,
of t h e deviations f r o m the TKS resulting f r o m the p r o p e r t i e s of the p r a c t i c a l
i n s t r u m e n t s used f o r interpolation between fixed points. The t e m p e r a t u r e s c a l e
covered by F i g u r e 6, is divided into s i x r a n g e s according to the techniques used
f o r determining thermodynamic t e m p e r a t u r e s .

B. PRACTICAL TEMPERATURE SCALES EMPLOYED BY NBS FOR THE

CALIBRATION OF TEMPERATURE -MEASURING INSTRUMENTS

At NBS the International P r a c t i c a l T e m p e r a t u r e Scale (IPTS) i s r e a l i z e d

to s e r v e a s a common b a s i s f o r defining t e m p e r a t u r e s in t h e United States.
Below the lower limit of t e m p e r a t u r e s defined by the IPTS at 90°K (-183"C),
a second s c a l e , known as the NBS P r o v i s i o n a l Scale of 1955 (NBS 1955 Scale),
has b e e n devised f o r u s e down t o about 12°K. In the range 2.0 t o 5.22"K a
t h i r d s c a l e , known as the T58 Scale (helium 4 vapor p r e s s u r e ) , is a l s o m a i n -
tained. Recently the gap between 5 and 1 2 ° K h a s been bridged b y a s c a l e b a s e d
upon work with the newly developed NBS acoustic t h e r m o m e t e r . Calibration
s e r v i c e s , provided f o r government agencies and p r i v a t e organizations and indi-
viduals, a r e b a s e d upon t h e s e s c a l e s .

The solid c u r v e s in the c h a r t of F i g u r e 7 r e p r e s e n t the a c c u r a c y with which

the t h r e e s c a l e s a r e r e a l i z e d , using the specified i n s t r u m e n t s of interpolation
between the defining t e m p e r a t u r e s of the s c a l e s . The dashed l i n e s shown a s -
signed l i m i t s of e r r o r for widely used calibration s e r v i c e s . These l i m i t s of
e r r o r a r e l a r g e l y judgment-type limits b a s e d upon e s t i m a t e d magnitudes of the
known s o u r c e s of e r r o r . In n e a r l y all c a s e s t h e r e a r e insufficient data of a

-
LME C Me mo - 6 8 - 10
27
LMEC-Memo-68- 10
28
 - *
-
N B S CAPABILITY IN REPRODUCING TEMPERATURE SCALES
-.I= ACCURACIES BASED UPON LIMITS OF ERROR ASSIGNED TO CALIBRATION RESULTS

DEGREES CELSIUS (CENTIGRADE 1

ONE - 262 - I83 0 630 1063 4000
PART
IN + NBS 1955 IPTS

I'0
PLATINUM RESISTANCE THERMOMETER
>- STANDARD PLATINUM THERMOCOUPLE
I-
-
Z
2
tr
10'
W
PLATINUM METAL THERMOCOUPLES
0 0
0- z
cx, 3 STANDARD OPTIC A L PYROMETER
I
c
0
lo3
BASE METAL THERMOCOUPLES
-
OPTICAL PYROMETERS

IO
I 10 IO0 1000 10,000 100,000
TEMPERATURE,O K
5-2- 68 76 94-55212
Figure 7. Calibration of Temperature-Measuring Instruments
kind which will p e r m i t s t a t i s t i c a l a n a l y s i s of the contribution of a p a r t i c u l a r
potential s o u r c e of e r r o r . 63
In s e v e r a l t e m p e r a t u r e r a n g e s , w o r k is c u r r e n t l y in p r o g r e s s whose p u r -
pose is the improvement and extension of calibration s e r v i c e s f o r t e m p e r a t u r e -
measuring instruments. At -183°C (90"K), the t e m p e r a t u r e of the oxygen point,
a p p a r a t u s is being developed which will m a t e r i a l l y improve the a c c u r a c y with
which t h i s point on the IPTS is realized. F o r use at high t e m p e r a t u r e s , a photo-
e l e c t r i c p y r o m e t e r has been developed which will improve the NBS r e a l i z a t i o n
of the IPTS above 1063°C (1945°F) (gold point). T h i s i n s t r u m e n t s p e r m i t s the
m o r e a c c u r a t e calibration of c o m m e r c i a l photoelectric p y r o m e t e r s which a r e
now becoming available. In addition, t h e development of s t a n d a r d s and facilities
f o r the calibration of h i g h - t e m p e r a t u r e thermocouples is a t a n advanced stage.

C. NBS PHOTOMETRIC STANDARDS

The c u r r e n t s y s t e m of photometric units and s t a n d a r d s i s b a s e d on the

luminance (candela/cm') of a blackbody at the t e m p e r a t u r e of freezing platinum
(2042"K), which is reproducible to within about 0.5%. The candela is defined
2
as the luminous intensity of 1/60th of 1 c m of projected a r e a of such a r a d i a t o r .
The luminous flux of o t h e r s t a n d a r d s o u r c e s ( r a t e of e n e r g y radiation in lumens)
i s t h e i n t e g r a l of the product of monochromatic luminance t i m e s its r e l a t i v e
luminous efficiency, taken over all wavelengths of visible s p e c t r u m , and con-
ventionally r e f e r r e d to the equivalent color t e m p e r a t u r e of a fictitious blackbody.
The uncertainty of luminous intensity of a s t a n d a r d s o u r c e ( f l u x reaching unit
a r e a of a unit s p h e r e ) is a l s o plotted a g a i n s t c o l o r t e m p e r a t u r e , since that i s a
m o r e i m p o r t a n t influence than the variation of intensity with the i n v e r s e square
of d i s t a n c e . F l u o r e s c e n t l a m p s t a n d a r d s , which have m e r c u r y l i n e s superimposed
on a continuum, a r e so different in s p e c t r a l distribution f r o m t h e r m a l r a d i a t o r s
r e l a t i v e to which they a r e c a l i b r a t e d that t h e i r photometric a s s i g n m e n t s a r e un-
c e r t a i n by about 270, with the uncertainty in t h e photometric a s s i g n m e n t s of in-
candescent lamp s t a n d a r d s between t h e s e two values of uncertainty. F i g u r e 8
is a graphic i l l u s t r a t i o n of t h e s e u n c e r t a i n t i e s .

Together with o t h e r national standardizing l a b o r a t o r i e s , NBS is i n v e s t i -

gating the feasibility of placing the s y s t e m of photometric units and s t a n d a r d s
on a r a d i o m e t r i c b a s e in which radiant flux of a given wavelength in the visible
63
LME C -Memo -68 - 10
30
 *-
ONE
PART PE CENT
IN I I I I I I

t
I I I 1 I I

0 PLATINUM BLACKBODY 3.2%

500 INCANDESCENT LAMPS
A
0 0'
- ACCURACYJ BLACKBODY

y
2
3 tPLATINUM
2 0 0 BLACKBODY+
H
0 0

H
0 PRECISloN
m ACCURACY
LUMINOUS INTENSIT7
3.5%

0
I
6 a 0 0 I%
'I w HITE" "DAY LIGHT"
00
I
w
0
FLUORESCENT FLUORESCENT
LAMPS LAMPS

a a 2%
I 1 I I I I I I I I I I

2000 3000 4000 5000 6000 7000

COLOR TEMPERATURE, O K
5-2-68 7694-552I 3

Figure 8. P r e c i s i o n and Accuracy of NBS Photometric Standards

region of the s p e c t r u m would be a s s i g n e d a value of luminous efficacy (for
example, 680 l u / w at 555 n a n o m e t e r s ) . The goal is to attain a reproducibility @
b e t t e r than about 0.25. In addition, NBS is investigating a r a d i o m e t r i c p r o -
c e d u r e f o r assigning photometric values to f l u o r e s c e n t l a m p s which, it is hoped,
will reduce the uncertainty of t h e s e values to l e s s than 1%.

D. CALIBRATION OF TEMPERATURE -MEASUREMENT INSTRUMENTS

Calibration is defined as the p r o c e s s of t r a n s f e r r i n g information by com-

p a r i s o n ; the m o r e d i r e c t the c o m p a r i s o n , t h e m o r e r e l i a b l e the calibration. In
calibrating t e m p e r a t u r e m e a s u r e m e n t d e v i c e s the b a s i c question to be asked is:
when a given environment is at a c e r t a i n thermodynamic s t a t e (the state defined
by the P V = RT relationship) what does t h e t e s t t h e r m o m e t r i c device i n d i c a t e ?

The most accepted method c u r r e n t l y employed f o r calibrating t h e r m o m e t r i c

devices i s to u s e a constant t e m p e r a t u r e bath (e. g . , oil bath, i c e bath, salt bath)
to provide the calibration environment. The calibrating bath should be one of
high t h e r m a l i n e r t i a (high heat content) s o t h a t minor e x t e r n a l perturbations will
not significantly affect the calibrating environment, and so that the heat l o s s can
b e controlled to a high d e g r e e of p r e c i s i o n . A r e p r e s e n t a t i v e ice-bath calibration
f i x t u r e i s i l l u s t r a t e d in F i g u r e 9.

The calibration t e m p e r a t u r e s ( s e e F i g u r e 1) a r e obtained by employing a

calibration point cell, such a s a t r i p l e point ( w a t e r ) cell o r a n aluminum cell
( s e e F i g u r e l o ) , in a t e m p e r a t u r e bath. The p r i m a r y s t a n d a r d s and devices
to be c a l i b r a t e d a r e placed i n t h e cell in such a manner as to e n s u r e a n i s o t h e r -
m a l condition within the cell. F o r t e m p e r a t u r e s at the melting points of m e t a l s ,
f o r instance, the t e m p e r a t u r e of the bath is r a i s e d a few d e g r e e s above the Cali-

b r a t i o n point and held t h e r e until a l l the m e t a l in the cell i s melted. The bath
is then allowed t o cool slowly. An i s o t h e r m a l condition will be obtained when
the s y s t e m a r r i v e s at the melting point t e m p e r a t u r e of the m e t a l at which t i m e
the heat l o s s f r o m the bath will be supplied by the heat of fusion of the metal.
At this point the devices being c a l i b r a t e d will indicate a constant reading even
though h e a t i s still being removed f r o m the s y s t e m . F i g u r e 11 i l l u s t r a t e s a
type of f u r n a c e used in m e t a l f r e e z e point calibration.

LMEC-Memo-68-10
32
 n-SUPPORT STAND

THERMOMETRIC
THERMOMETRIC
DEVICE SUPPORT
DUST COVER
SUPPORT PLATE

CLAMP

DEWAR FLASK

FLOW DIRECTION
U U
5-2-68 7694-55214

F i g u r e 9. Representative Ice-Bath Calibration Fixture

.E CAP

"

IBLE

5-2-68 7694-55215

Figure 10. Cross-Section of F r e e z i n g

Point Standa r d Cell (Aluminum)

LMEC-Memo-68 - 10
33
 A PORCELAIN PROTECTING TUBE
B REFRACTORYFURNACETUBE
C HEATING ELEMENT (80 NICKEL, 2 0 CHROMIUM)
D GRAPHITE DIAPHRAGMS
E CONTROL THERMOCOUPLE (CHROMEL-ALUMEL)
F FURNACE CONTROL TC TERMINALS
G GRAPHITE POWDER
H GRAPHITE CRUCIBLE
I SHEETSTEEL
J FEEDTHROUGH
K HEATER POWER LINE
L INSULATING BLOCKS
M FREEZING-POINT M E T A L
N CAST-IRON BASE
I/.
0 POWDERED DIATOMACEOUS EARTH INSULATION

t--,5_41L J L.2!? _.I_

SCALE IN CENTIMETERS
5-2-68 7694-55216

F i g u r e 11. F u r n a c e Used i n Calibrating

Thermocouples at F r e e z i n g Points of
Metals

By recording the readings of the devices being calibrated at a number of

check points o v e r the range of i n t e r e s t , a calibration c u r v e can be a r r i v e d at
f r o m which intermediate t e m p e r a t u r e points may be interpolated. It i s not
within the scope of this r e p o r t t o define calibration p r o c e d u r e s f o r any p a r t i c -
u l a r device. The preceding discussion is intended t o provide the r e a d e r with
a n understanding of the b a s i c principle involved. F o r f u r t h e r details s e e the
specific Standards Laboratory Calibration P r o c e d u r e f o r the device of i n t e r e s t .
See Reference 2 for a f u r t h e r discussion of interpolation equations and r e s p o n s e ,
r e c o v e r y and h e a t - t r a n s f e r ' considerations.

Calibration a t e x t r e m e l y high t e m p e r a t u r e s generally r e q u i r e s a vacuum

c h a m b e r with a view p o r t f o r a n optical p y r o m e t e r . F i g u r e 12 i l l u s t r a t e s a
typical,t e s t facility f o r high t e m p e r a t u r e thermocouple t e s t and calibration.

LME C -Memo -68 - 10

34
 OPTICAL
PYROMETER
VIEW PORT
IONIZATION
GAGE J--GETTER-ION
PUMP

BLACK BODY /Tam W,o COIL

CAVITY
t
-Ta RADIATION
SHIELDS
ISOTHERMAL
TEST BLOCK
-COLD WALL VACUUM
CHAMBER

, BLOCK-

i BATH
I COPPER LEADS
"1
M O V / ! B L E ~
REFEREE
TC
AND SWITCHES

HOUSlNG
'
7
K-3 POTENTIOMETER
-MOVABLE
1
-MOVABLE
COMPRESSION SEAL

REFEREE TC

EXTERNAL
MAGNET

5-2- 68 7694-55217

Figure 12. Schematic of Drift T e s t Facility

LME C -Memo - 68 - 1 0
35
 V . TEMPERATURE MEASUREMENT TECHNIQUES AND INSTRUMENTS

As stated previously, any m a t e r i a l physical c h a r a c t e r i s t i c which v a r i e s

reliably with t e m p e r a t u r e m a y be used a s a t e m p e r a t u r e m e a s u r e m e n t device.
This f a c t has given r i s e t o numerous devices and techniques over the y e a r s .
Some a r e highly specialized while others enjoy a wide scope of application.
Some a r e designed to r e g i s t e r one t e m p e r a t u r e , o r a v e r y n a r r o w band, while
o t h e r s m a y be applicable over a v e r y wide range, and still other techniques
w e r e developed f o r u s e at e i t h e r e x t r e m e of the t e m p e r a t u r e range. While it
is the intention of t h i s document to be as inclusive a s possible, the amount of
s p a c e allocated t o e a c h technique will be generally proportional to its relative
importance as applied t o m e a s u r e m e n t s i n liquid m e t a l high f l u x nuclear r e a c t o r s .

A. THERMOELECTRIC THERMOMETRY

1. Thermoelectricity

In 1 8 2 1 , Seebeck discovered the t h e r m o e l e c t r i c emf named after him.

Thermodynamically, t h e Seebeck effect is actually the algebraic s u m of the
P e l t i e r and Thomson effects. Whenever t h e junctions f o r m e d of two d i s s i m i l a r
homogeneous m a t e r i a l s a r e exposed t o a t e m p e r a t u r e difference, a n emf will b e
generated which is dependent on that t e m p e r a t u r e difference and a l s o on the
t e m p e r a t u r e l e v e l and the m a t e r i a l s involved. Since this emf i s m e a s u r a b l e
either by m e a n s of a millivoltmeter o r potentiometer, it provides a means of
m e a s u r i n g t e m p e r a t u r e differences. If a r e f e r e n c e t e m p e r a t u r e such a s an ice
bath is established for one of the junctions, and the other junction is exposed t o
a n environment a t s o m e unknown t e m p e r a t u r e , then the e m f a s r e a d b y the indi-
cating i n s t r u m e n t will v a r y d i r e c t l y , and only, with the unknown t e m p e r a t u r e .
In o r d e r to take advantage of t h i s t h e r m o e l e c t r i c t h e r m o m e t e r , a s u c c e s s f u l
effort h a s been made t o establish many useful e m p i r i c a l relationships and to
develop an advanced m a t e r i a l s technology.

A thermocouple i s a s y s t e m of two w i r e s , A and B, welded together to

f o r m a measuring junction with the f r e e end constituting the r e f e r e n c e junction.
Its successful u s e i s based on the application of t h r e e fundamental laws, which
have been established experimentally beyond a reasonable doubt. The t h r e e
laws m a y b e combined and stated a s follows: t h e algebraic s u m of the t h e r m o -
e l e c t r i c e m f ' s generated in any given c i r c u i t containing any number of d i s s i m i l a r

LMEC -Memo -68 - 10

37
homogeneous m e t a l s is a function only of the t e m p e r a t u r e s of the junctions.
The important point i s that the magnitude of the emf i s independent of the
p r e s e n c e of a third m a t e r i a l as long a s t h e junctions with the t h i r d m a t e r i a l
a r e at the s a m e t e m p e r a t u r e .

F o r a m o r e detailed discussion of t h e r m o e l e c t r i c theory and i t s governing

laws s e e Reference 3 , Section 6 .

2. Advantages and Limitations of Thermocouples

Some of the advantages of the thermocouple a r e :

1) Stability

2) Lack of h y s t e r e t i c effects i n g e n e r a l

3) Small physical sampling s i z e

4) E l e c t r i c a l signal generation

5) Flexibility a s t o physical s i z e , orientation, positioning

6) Wide range of operation

7) Adaptability f o r measuring g a s , liquid or solid t e m p e r a t u r e s

8) Insignificance of c o r r e c t i o n to readings

9) Resistance t o c o r r o s i o n , e r o s i o n , e t c . Readings not affected until

phase changes a r e essentially complete in the m a t e r i a l s of which it
is composed (for p u r e m a t e r i a l couples)

10) E a s e of application

11) Low cost of m a t e r i a l generally

12) L a r g e body of experimental technique e x i s t s .

Thermocouples r e t a i n many of t h e i r advantages even a t v e r y high t e m p e r a -

t u r e s , especially t h e i r stability under c o r r o s i v e influences, a s compared with
m o s t other techniques of t e m p e r a t u r e m e a s u r e m e n t . T h e r e f o r e they appear to
be m o s t a t t r a c t i v e high t e m p e r a t u r e m e a s u r i n g devices.

Among the disadvantages of the thermocouple a r e : the purely e m p i r i c a l

calibration c u r v e s , cold junction c o r r e c t i o n s , special m a t e r i a l s used in com-
position (such a s alloys) which make d r i f t of readings possible o n change of
A
composition, and relatively small dc e l e c t r i c a l signal outputs.

LME C -Me mo -6 8 - 10
38
 The main limitations on the u s e of thermocouples a t high t e m p e r a t u r e s
involve the useful lifetime of the sensing element and the r a t e of contamination
o r change of calibration. E a c h application and environmental condition will
dictate the useful lifetime, and the a c c u r a c y d e s i r e d will d e t e r m i n e the allow-
able d r i f t . Acceptable lifetimes m a y v a r y f r o m seconds t o y e a r s . F o r example,
in m e a s u r i n g liquid m e t a l t e m p e r a t u r e s it m a y be sufficient to r e a d a t e m p e r a -
t u r e by a dip t e s t , w h e r e a s i n furnace applications thermocouples may have to
be installed i n inaccessible locations.

In the main it m a y be said that raising the operating t e m p e r a t u r e of a couple

will shorten its life at a p r o g r e s s i v e l y g r e a t e r r a t e . Generally, operating the
thermocouple in a noncorrosive a t m o s p h e r e (at any t e m p e r a t u r e ) will i n c r e a s e
its life greatly.

Limitations in a neutron environment c o n c e r n the transmutation of material

by neutron capture, hence change i n calibration. Rhodium subjected t o neutron
bombardment converts t o palladium, the resulting f i s s i o n product d e c a y s .
Iridium a p p e a r s completely u s e l e s s b e c a u s e of its r e a d i n e s s t o t r a n s m u t e . The
conversion of rhenium t o o s m i u m p r e s e n t s s o m e problems with t h i s m a t e r i a l
f o r long t e r m u s e i n high flux environments.

3. M e a s u r e m e n t s and Calibration

Any of t h e s t a n d a r d techniques f o r the m e a s u r e m e n t of emf m a y b e used

as long as they have the requisite a c c u r a c y . However, at high t e m p e r a t u r e s
those s c h e m e s which r e q u i r e drawing a c u r r e n t f r o m the c i r c u i t should be
avoided. T h i s is because p r o g r e s s i v e r e s i s t a n c e changes of the thermocouple
and leads due to physical and chemical aging o r c o r r o s i o n must be expected.
If a multiple channel r e c o r d e r is t o be employed it should be of the potentio-
m e t r i c type.

F o r any thermocouple, the emf v s t e m p e r a t u r e relationship c a n always be

generated as a c c u r a t e l y a s d e s i r e d , depending on how carefully the calibration
is p e r f o r m e d . However, thermocouple r e f e r e n c e t a b l e s a r e m o s t commonly
used. T h e s e tables contain r e f e r e n c e values which r e p r e s e n t , i n both f o r m
and magnitude, the nominal c h a r a c t e r i s t i c s of p a r t i c u l a r types. T h u s , even
assuming t h a t all the n e c e s s a r y precautions have been taken to eliminate
reading and i n s t r u m e n t e r r o r s , s t r a y e m f ' s , e t c . , t h e r e i s a limit of accuracy

LME C -Me mo -68 - 10

39
connected with all c o m m e r c i a l l y available thermocouples when r e f e r e n c e t a b l e s
a r e used. These e r r o r limits a r e a function of the type of thermocouple, its
w i r e gauge, and the t e m p e r a t u r e r a n g e and environmental conditions i n which
it will b e used. Despite t h e b e s t that the suppliers c a n do in the way of quality
.
I
.

control, these e r r o r s can r e a c h s e v e r a l percent (type J". o r K below -100°C and

type T below -60°C). More typical values a r e 3 / 4 % f o r types J o r K above 250°C
and type T above 100°C, and 1/4% f o r types R and S f r o m 550 to 1500°C.

Lf it is not d e s i r e d t o locate the voltage indicator c l o s e to the position of the

measuring junction, then copper w i r e m a y be used t o connect the indicator t o
the junctions. This is p r o p e r p r o c e d u r e , no m a t t e r what the m a t e r i a l s , a s long
a s the extension w i r e junctions a r e held at a constant r e f e r e n c e t e m p e r a t u r e .
In m o s t industrial applications, it is c u s t o m a r y t o employ cold-junction c o m -
pensation, and e i t h e r a bimetallic-spring a r r a n g e m e n t o r a t e m p e r a t u r e -
sensitive r e s i s t o r b r i d g e c i r c u i t is used t o compensate f o r changes i n t h e r m a l
emf occurring at this new r e f e r e n c e junction. In t h i s c a s e , the thermocouple
w i r e should b e used d i r e c t l y w h e r e possible. If, a s is often the c a s e , the ex-
pense entailed by long runs is e x c e s s i v e , then thermocouple extension w i r e s
m a y be used. W i r e s of special composition a r e available for types R , S, and
K thermocouples. They provide a match f o r the p a r t i c u l a r thermocouple emf
at the probable t e m p e r a t u r e of the .junction between the thermocouple and the
extension leads. Types J, E , and T a r e used a s t h e i r own extension w i r e s ,
although a change i n w i r e gauge ( f r o m a number 8 to a number 18 gauge, f o r
example) m a y be appropriate.

If the m e t e r i s a millivoltmeter, it will be found to consist of a galvanometer

with a pointer which moves a c r o s s a s c a l e graduated in e i t h e r mv, o r in " F , o r
O C. Because the galvanometer actually m e a s u r e s a s m a l l c u r r e n t (typically
50 pa to 1 ma) produced by the t h e r m a l e m f , and since t h i s c u r r e n t depends on
t h e t o t a l r e s i s t a n c e in the c i r c u i t , the m e a s u r e m e n t is c o r r e c t only if the r e s i s -
tance r e m a i n s constant a f t e r calibration. As previously mentioned, t h i s r e s i s -
tance i s quite apt to change; t h i s phenomenon, along with changes in pivot f r i c -
tion, spring constant, and magnetic-field s t r e n g t h i n the m e t e r , w i l l introduce
a reading e r r o r . The potentiometer avoids these difficulties, and with its much

K h s t r u m e n t Society of A m e r i c a thermocouple designations: Types S, R , J , T,

K , and E.

LME C -Memo -68 10 -

40
g r e a t e r definition of scale, provides g r e a t l y i n c r e a s e d precision. The fact
r e m a i n s , however, that the low cost, simplicity, and d i r e c t n e s s of t e m p e r a -
t u r e indication of the millivoltmeter p r e s e r v e s f o r it a v e r y useful place in the
a r e a of industrial t h e r m o m e t r y .

As i n the c a s e of any t r a n s d u c e r , many inconspicuous e r r o r s i n the f i n a l

m e a s u r e m e n t c a n r e s u l t f r o m poor instrumentation p r a c t i c e s . Thermocouples,
p a r t i c u l a r l y when used with electronic a m p l i f i e r s , indicators, r e c o r d e r s , and
c o n t r o l l e r s , a r e prone t o ground-loop leakage e r r o r s , problems with s t r a y
magnetic and e l e c t r i c fields, e t c . If p r o p e r c a r e is taken and if a c c u r a t e indi-
c a t o r s a r e used in a s s o c i a t i o n with stable, well-made thermocouples, then it
m a y be stated that the s u c c e s s attained i n the m e a s u r e m e n t of t e m p e r a t u r e with
thermocouples depends a l m o s t entirely upon the ability of the o b s e r v e r to bring
the thermocouple junctions t o the d e s i r e d t e m p e r a t u r e s .

F i g u r e s 1 3 through 16 i l l u s t r a t e s o m e typical thermocouple c i r c u i t s used

t o m e a s u r e t e m p e r a t u r e ; they a r e a potentiometric c i r c u i t , differential t e m p e r -
a t u r e and m e a n t e m p e r a t u r e c i r c u i t s , and a thermopile c i r c u i t .

Calibration of a thermocouple is usually accomplished by c o m p a r i s o n with

a standardized thermocouple in the m o d e r a t e t e m p e r a t u r e r a n g e s and against
a n optical p y r o m e t e r i n the higher r a n g e s . Calibration m u s t be done under
environmental conditions which a r e c l o s e a s possible to those of the application,
allowing t h e couples to come to equilibrium. Standard couples m a y be certified
by the N B S and a r e usually standardized by taking a number of f r e e z i n g point
c u r v e s of s e l e c t e d chemical elements.

In using the optical p y r o m e t e r as a standard, the u s u a l precautions con-

cerning intervening v a p o r s , e m i s s i v i t i e s , and collimation must be considered.

F o r f u r t h e r detail on calibration p r o c e d u r e s and precautions to be observed

i n thermocouple calibration s e e R e f e r e n c e s 1 and 4.

M e a s u r e of Thermocouple Quality by T i m e Domain Reflectometry. T i m e domain

reflectometry h a s been investigated a s a possible tool t o be u s e d t o evaluate the
quality of a complete metal-sheathed thermocouple.

M e a s u r e m e n t s w e r e made with a Hewlett-Packard Model 1415 T i m e Domain

Reflectometer plug-in installed in a Hewlett-Packard Model 140A Oscilloscope.

LMEC-Memo-68-10
41
- J1
t.

B
r--1

>
t3

ICE-POINT
I

THERMOMETER.
I

I
I

ICE BATH
REFERENCE
t2

VACUUM F L P
cu

MATERIAL A

1
COTTON PLUGS
HIGH GAIN

3-
NULL
METER

COPPER
MATERIAL B
PRECISION
POTENTIOMETER

CORKSTOPPER
SHEET M E T A L
CALIBRATED
VOLTAGE

ICE AND WATER

5-2-68 7694-55218

F i g u r e 13. Typical Ice Bath for Reference Junctions

LMEC-Memo- 68- 10
42
 MILLIVOLT
METER

JI J2

5-2-68 UNCL 7694 - 55219

F i g u r e 14. Differential Thermocouple
BAB and M e t e r M M e a s u r e the
T e m p e r a t u r e Difference t3 - t l

VOLTMETER M I L LIVO LT

C C

bd

J I

5-2-68UNCL 7694-55220 5-2-68 UNCL 7694 - 55221

F i g u r e 15. N Thermocouples i n F i g u r e 16. N Thermocouples i n P a r a l l e l
S e r i e s Acting as a Thermopile Providing a Measurement of the T e m -
.
p e r a t u r e Mean Among t l , t2. t n

LMEC-Memo- 68- 10
43
The technique of reflectometry c o n s i s t s essentially of applying a n ultra-fast
n
r i s e t i m e voltage s t e p t o the s y s t e m t o be t e s t e d and observing the reflections.
A reflection o c c u r s e a c h t i m e the s t e p encounters a n impedance change o r d i s -
continuity; t h i s reflection is added to the incident wave and is displayed on the
oscilloscope. The t i m e required f o r the r e t u r n of the reflection locates the
discontinuity. The shape and magnitude of the reflected wave indicate t h e
n a t u r e and magnitude of the discontinuity.

Reflectometry is at its b e s t in indicating and locating a c c u r a t e l y g r o s s

f a u l t s such a s opens and s h o r t c i r c u i t s , and a r e a s of significantly reduced i n -
sulation r e s i s t a n c e . It is l e s s effective in revealing fine-line f r a c t u r e s , p a r t i c -
u l a r l y when definition has been reduced by intervening cable. F u r t h e r details
of t h i s technique a r e covered i n Reference 5, Section II. J.

4. Thermocouple F a b r i c a t i o n

The fabrication of thermocouples has been accomplished by a l m o s t a s many

techniques as a r e known f o r bonding m e t a l s together. Some of t h e techniques
used have been soldering, brazing, welding, forging, electroplating, vapor
deposition, swaging, o r friction. Concentric tube and w i r e o r rod a r r a n g e -
m e n t s have been used where mechanical stability was i m p e r a t i v e . Surface tem-
p e r a t u r e m e a s u r e m e n t s have been made by plating o r tamping thermocouples
into s u r f a c e s , and a thermocouple h a s been made without junction, by dipping
two d i s s i m i l a r r o d s into a molten metal.

In m o s t c a s e s precautions must b e taken t o p r e v e n t the oxidation of t h e

joint and t o exclude foreign m a t e r i a l s which would weaken the mechanical
p r o p e r t i e s of the joint.

In m e a s u r i n g high g a s t e m p e r a t u r e s c a r e m u s t be taken to p r e v e n t radiation

l o s s e s f r o m the thermocouple. This is usually accomplished by encasing the hot
junction in porous metallic shields of low emissivity. Elaborate s c h e m e s have
s o m e t i m e s been used t o e n s u r e the s m a l l e s t radiation l o s s e s , such as installing
heating elements in the radiation shields to maintain the shield and couple a t the
same temperature.

F o r high t e m p e r a t u r e s the couple elements should be so constructed as t o

offer l e s s r e s i s t a n c e t o c o r r o s i o n a t the junction than along the elements them-
selves. This is to e n s u r e that c o r r o s i o n effects along the length of the couple
elements will not r e s u l t i n p a r a s i t i c emf's.

LMEC-Memo -68 -10

44
 F i g u r e s 17 through 26 i l l u s t r a t e some of the m o r e common thermocouple

@ fabrication configurations. F i g u r e 25 is not recommended f o r high a c c u r a c y

but r a t h e r f o r quick, low-cost installation.

5. Thermocouple Installation

Installation m u s t be done with c a r e t o be c e r t a i n that the junction is main-

tained a t the s a m e t e m p e r a t u r e a s the m a t e r i a l whose t e m p e r a t u r e is being
measured. Heat l o s s e s by conduction of the thermocouple l e a d s , and radiation
l o s s e s t o colder surroundings m u s t b e minimized. The heat capacity of the
thermocouple and its appurtenances m u s t b e s m a l l enough to allow the junction
t o follow t e m p e r a t u r e changes i n the medium a t a s a t i s f a c t o r y r a t e .

In addition, the thermocouple a s s e m b l y should be composed of m a t e r i a l s

which will r e s i s t physical o r c h e m i c a l effects that would change its calibration.
At v e r y high t e m p e r a t u r e s the p r o b l e m of physical and chemical c o r r o s i o n be-
c o m e s of paramount importance. Most metals experience r e c r y s t a l l i z a t i o n
and become e m b r i t t l e d . P h a s e changes a r e experienced, and chemical r e a c t i o n
rates i n c r e a s e exponentially. P r o t e c t i o n tubes o r wells to i s o l a t e the t h e r m o -
couple f r o m t h e environment a r e usually n e c e s s a r y . The thermocouple cannot
be physically removed after installation and operation a t high t e m p e r a t u r e s
without injury to the components. If possible, the thermocouple should b e o p e r -
ated in a n i n e r t a t m o s p h e r e such a s a r g o n , although even a r g o n o r helium may
c a u s e e m b r i t t l e m e n t of c e r t a i n metals (e. g . , tantalum).

Caution should be observed in the selection of i n s u l a t o r s for the couple

elements. Even if a m a t e r i a l is s a t i s f a c t o r y a t high t e m p e r a t u r e s f o r its insu-
lating p r o p e r t i e s , it m a y s t i l l r e a c t with the thermocouple e l e m e n t s at h i g h
temperatures. Typically, s o m e of the oxides will r e a c t to oxidize the couple
e l e m e n t s while freeing metallic vapors. T h e s e vapors m a y ultimately s h o r t
out the i n s u l a t o r s .

F o r leading the signal f r o m a thermocouple w i r e t o a m e a s u r i n g i n s t r u -

ment extension w i r e s a r e often used. T h e s e a r e w i r e s of the same relative
t h e r m a l e m f a s the thermocouple w i r e s . T h e composition of thermocouple
m a t e r i a l and extension leadwire m u s t have t h e s a m e t h e r m a l emf relationship
if spurious emf's a r e not to be introduced into the circuit. F o r high t e m p e r a -
t u r e applications, w h e r e the cold junction is maintained at t h e point of exit f r o m

LMEC-Memo -68-10
45
t

5-2-68 7694 -55222

Q
F i g u r e 17. Single Thermocouple - Double-bore C e r a m i c Insulators

5- 2-68 7694-55223
F i g u r e 18. Single Thermocouple - Fish-spine C e r a m i c Insulators

I
5-2-68 7694-55224

Figure 19. Double Thermocouple - Four-hole C e r a m i c Insulators

5-2-68 7694-55225

F i g u r e 20. Exposed Loop Thermocouple

0) WITH FIBERGLAS INSULATED LEAD, b) W I T H STAINLESS S T E E L B R A I D E D LEAD,

NO SUPPORT STAINLESS S T E E L SUPPORT
5-2-68 7694-55226

F i g u r e 21. Gasket Thermocouple

5-2-68 7694-55227
F i g u r e 22. Mixture Thermocouple

5-2-68 7694-55228'
F i g u r e 23. Shielded Thermocouple

LMEC-Memo-68- 10
46
 M E T A L JACKET

SEE
DETAILS
a) AND b)

M E T A L SHEATH

WELD
PLUG

WELD

CERAMIC PACKING.
D E T A I L a) D E T A I L b)
GROUNDED UNGROUNDED

5-2-68 UNCL 7694-55229

F i g u r e 24. Sheathed Thermocouple

5-2-68 UNCL / 7694-55230

F i g u r e 25. T h e r m o E l e c t r i c Co., Inc., Patented Pipe Clamp
Adapter (Patent No. 2, 752, 41 1 )

LMEC-Memo-68-10
47
 NITROGEN I N L E T WATER OUTLET

l - i n . OD THREADED
/GRAPHITE PLUG (+I POSITIVE TERMINAL
1 - i n . OD GRAPHIT
X 1/8-in. WALL T

/ \INSULATOR
3/8-in. DIA BORONATED
GRAPHITE ROD

5-2-68
\7(-)
WATER I N L E T

NEGATIVE TERMINAL
7694-55231A

F i g u r e 26. Boron Graphite /Graphite

Thermocouple, Coaxial Style

the hot region by a r t i f i c i a l cooling, o r d i n a r y copper w i r e s will suffice f o r

leading the signal to the m e a s u r i n g i n s t r u m e n t .

In one installation on the Sodium R e a c t o r E x p e r i m e n t (SRE) at Atomics

International it w a s found that epoxy can be u s e d successfully t o s e a l t h e r m o -
couple penetrations in the cold top region of a r e a c t o r shield plug. This tech-
nique p r e c l u d e s welding o r b r a z i n g on the sheath, thereby diminishing a poten-
t i a l h a z a r d of installation. Epoxy a d h e s i v e s a r e available f o r operation t o
550°F.

F o r fast r e s p o n s e , t h e r m o c o u p l e s using 0.5- and 1.0-mil w i r e have been

spotwelded d i r e c t l y t o the s u r f a c e of the media being monitored, using a s t o r e d
charge discharge welder. When t e s t e d by pulsing with a c u r r e n t and then r e -
cording the t i m e to decay, a typical t i m e constant of 2 m s w a s m e a s u r e d for a
0.5-mil Chromel-Alumel thermocouple.

6. Thermocouple M a t e r i a l s

Seebeck's original d i s c o v e r y of t h e r m o e l e c t r i c i t y w a s based on a c i r c u i t

using w i r e s of copper and antimony. Of all t h e p r a c t i c a l l y l i m i t l e s s combinations

LMEC-Memo-68-10
48
 of metals and alloys available since that t i m e to make thermocouples, relatively
@ few have been put to u s e . These have been chosen on the b a s i s of t h e i r t h e r m o -
,
e l e c t r i c power ( d E / d t ) t h e i r stability and reproducibility, t h e i r homogeneity,
relatively high e l e c t r i c a l conductivity and melting points, e a s e of fabrication and
cost.

The emf of any metal used a s thermocouple element against any o t h e r may
b e obtained by integration of the t h e r m o e l e c t r i c powers of the two m e t a l s .
Table 1 is a listing of m e t a l s , s o a r r a n g e d that each item in the list i s t h e r m o -
e l e c t r i c a l l y negative with r e s p e c t to all those below it. F o r f u r t h e r detailed
information on thermocouple m a t e r i a l s s e e Reference 6.

TABLE 1
THERMOELECTRIC SERIES OF SELECTED
METALS AND ALLOYS

100°C I 500°C 900°C

Antimony Chr omel -P Chromel-P

C h r o m e l - P (90Ni-1 OCr) Nichrome Nic h rome
Iron Copper Silver
N ic h r o m e Silver Go1d
Copper Gold Iron
Silver Iron 9OPt-1ORh
90Pt -10Rh 9 O P t- 1ORh Platinum
Platinum Platinum Cobalt
Palladium Cobalt Alu me 1
Cobalt Palladium Nickel
Alumel (94Ni - 3Mn- 2A1- 1Si) Alumel Palladium
Nickel Nickel Constantan
Cons tantan (57 Cu -43Ni) Con stant a n
Cope 1 Cope1
Bismuth

LME C -Memo -68 - 10

49
 The thermocouple combinations m o s t commonly used b e a r the Instrument
Society of A m e r i c a designations - t y p e s S, R, J, T, K, and E. With the ex-
ception of the noble m e t a l thermocouples, the f i r s t named of the thermocouple
p a i r is usually the positive leg.

F o r f u r t h e r d e t a i l s o n thermocouple c h a r a c t e r i s t i c s and p e r f o r m a n c e s e e
R e f e r e n c e 7.

a. Type S. Scientifically speaking, the type S, o r platinum-platinum t1070

rhodium thermocouple i s the m o s t important of the thermocouples now i n use.
Often called the Le Chatelier couple, it is u s e d f o r defining the ITPS f r o m
630.5 t o 1063°C. T h e interpolation equation, assuming a r e f e r e n c e junction of
O'C, is

2
E = a t b t t ct

w h e r e E is in p v . The constants a , b , and c a r e determined by calibration at

t h e f r e e z i n g points of gold and s i l v e r and by a platinum r e s i s t a n c e t h e r m o m e t e r
reading at 630.5"C. Although the equation is r e s t r i c t e d to the range which it
s e r v e s to define, the type S couple m a y be used i n oxidizing a t m o s p h e r e s f o r
p r e c i s i o n m e a s u r e m e n t s between 0 and 1500°C and f o r short t i m e s and with
special precautions t o 1650°C. Its sensitivity is about 11 p v/OC at 1000°C.

b. Type R. The alloy Pt87-Rh13, with its approximately 20% higher output,
is used to s o m e extent with platinum in place of Pt9O-RhlO. This h a s been
designated type R.

c. Type T . Copper-constantan, the type T thermocouple, h a s been a popular

s e n s o r i n industrial and l a b o r a t o r y applications w h e r e a c c u r a t e t e m p e r a t u r e
m e a s u r e m e n t s a r e r e q u i r e d in the -200 to t 250°C range. Within t h e s e limits,
i t s t h e r m o e l e c t r i c power ranges f r o m 15 to 60 p v / " C. This sensitivity, com-
bined with its low cost and the high homogeneity obtainable in copper w i r e ,
m a k e s it the p r e f e r r e d thermocouple in its range. Above 35OoC, the copper
oxidizes too rapidly to give s a t i s f a c t o r y s e r v i c e . With p r o p e r calibration and
suitable precautions, the type T can be u s e d a s low a s 11°K. It should b e noted
that the constantan used i n t h i s couple (known a s "Adams Constantan") i s not the
s a m e as t h a t used with iron-constantan thermocouples, because of different volt-
age r e q u i r e m e n t s. A

LME C -Memo -68 - 10

50
 d. Type K. Type K was used originally to designate only the Chromel-Alumel
@ thermocouple. T h e r e a r e now two o t h e r thermocouples in this c l a s s , the
Kanthal P-Kanthal N , and Tohel-Nial. The main constituent of all the type K
m a t e r i a l s is nickel, which is p r e s e n t i n amounts ranging f r o m 90% in the
positive-leg compositions. Chromium i s a n i m p o r t a n t element in t h e positive-
leg m a t e r i a l ; manganese, silicon, aluminum, i r o n , cobalt, and carbon a r e
p r e s e n t i n varying amounts i n all of them. The t h e r m o e l e c t r i c power of the
type K couples is f a i r l y constant, averaging 40 p v / " C . It h a s v e r y good oxi-
dation r e s i s t a n c e , which p e r m i t s its continuous u s e at t e m p e r a t u r e s up to 1200"C
and, for limited t i m e s , a s high a s 1300°C. However, it i s subject to the s a m e
limitations a s the platinum couples with r e s p e c t t o u s e in reducing a t m o s p h e r e s
a t such high t e m p e r a t u r e s . In addition, it can be used a s low as -200°C; how-
e v e r , its m o s t i m p o r t a n t i n d u s t r i a l application is in the 700 t o 1250°C range.

Inconel sheath Chromel-Alumel thermocouples t e s t e d in sodium have d e m -

o n s t r a t e d a mean deviation of about 8°F at t e m p e r a t u r e s of 1100 to 1500°F f o r
4000 to 5000 h r and a m e a n deviation of 2 0 ° F at 1800°F f o r 5000 h r . R e f e r e n c e 5
indicates t e s t r e s u l t s of Chromel-Alumel thermocouples to 2 2 0 0 ° F for thousands
OS ho;ir 5:.
e. Type J. The type J , o r iron-constantan, thermocouple i s the m o s t widely
u s e d of all i n d u s t r i a l thermocouples. Constantan is an alloy of copper and
nickel, ranging f r o m Cu50 Ni50 to Cu65Ni35, but f o r t h e r m o e l e c t r i c p u r p o s e s
it h a s a n approximate composition of Cu57Ni43. Small p e r c e n t a g e s of m a n -
ganese and i r o n and t r a c e i m p u r i t i e s such as c a r b o n , magnesium, silicon, and
cobalt a r e also u s e d . The r e l a t i v e l y high t h e r m o e l e c t r i c power ( i n c r e a s i n g
f a i r l y uniformly f r o m about 27 p v / " C at -190°C t o 6 3 p v / "C at 8OO0C), c o m -
p r a t i v e l y low c o s t , and its adaptability to both oxidizing and reducing a t m o -
s p h e r e s a r e r e s p o n s i b l e f o r its popularity.

f. Type E . The Chromel-constantan, o r type E , thermocouple is a r e l a t i v e

newcomer to the field. Over its range of 0 to 9OO0C, it h a s v e r y good stability
and the highest t h e r m o e l e c t r i c power (as high as 81 p v / " C at 500°C) of the
commonly used thermocouples. T h e s e c h a r a c t e r i s t i c s make it useful in dif-
f e r e n t i a l t e m p e r a t u r e m e a s u r e m e n t s and in t h e r m o p i l e s requiring high
sensitivity.

LME C -Memo -68 - 10

51
g. High T e m p e r a t u r e Thermocouples. F o r t e m p e r a t u r e s to 2500°C the
W / W -26Re thermocouple h a s the highest output and sensitivity. Reference 5
indicates t e s t r e s u l t s of the W -5Re/W-26Re useful to 2800°F for a t l e a s t 1,000 h r
and at 2300°F f o r a l m o s t 10,000 h r . Molybdenum-columbium thermocouples
w e r e developed f o r u s e in a n u c l e a r radiation environment b e c a u s e of t h e i r low
nuclear c r o s s -section. R e f e r e n c e 5, Section II.1 d i s c u s s e s the Mo-Cb t h e r m o -
couple i n f u r t h e r detail. F o r highest stability and p r e c i s i o n types R and S ( s e e
preceding p a r a g r a p h s a and b) a r e used. Also, p e r R e f e r e n c e 5, the d i s c u s s e d
t h e r m o c o u p l e s indicated operation at 1950 t o 2 0 0 0 ° F f o r 16,000 h r in 1 /8-in. OD
Cb-1 Z r alloy sheathing with alumina insulation.

h. Others. T h e r e a r e many o t h e r thermocouple combinations available f o r

special purposes. In t e r m s of everyday u s e , they r e p r e s e n t but a s m a l l f r a c t i o n
of thermocouple applications, but t h e r e a r e s e v e r a l worthy of mention f o r t h e i r
s e r v i c e a t e x t r e m e s of t e m p e r a t u r e . F o r the cryogenic range below 9 0 ° K , gold
t2.170 cobalt v s copper o r n o r m a l s i l v e r is outstanding. I r i d i u m / i r i d i u m 40 -
rhodium 60, and g r a p h i t e vs doped graphite have been u s e d a t t e m p e r a t u r e s in
t h e 2000 to 3000°C range.

B. RESISTANCE THERMOMETRY

R e s i s t a n c e t h e r m o m e t e r s can be t h e m o s t a c c u r a t e of all t e m p e r a t u r e
sensing d e v i c e s , permitting m e a s u r e m e n t s t o be made within a n a c c u r a c y of
about 10-4"C at r o o m t e m p e r a t u r e . T h e i r operation is b a s e d on the f a c t that
t h e r e s i s t a n c e offered to the p a s s a g e of a n e l e c t r i c c u r r e n t by any m a t e r i a l is
dependent on its t e m p e r a t u r e . Suitably chosen and p r e p a r e d m a t e r i a l s will
v a r y i n a well-defined and c a l i b r a t i b l e m a n n e r with t e m p e r a t u r e . The r e s i s -
tance v a r i a t i o n is usually m e a s u r e d with b r i d g e a r r a n g e m e n t s such a s the
Wheatstone, Kelvin, o r Mueller b r i d g e s . P o t e n t i o m e t r i c techniques (employing
c o n s t a n t - c u r r e n t s o u r c e s and p r e c i s i o n potentiometers) have a l s o b e c o m e popu-
lar. T h e r e a r e s p e c i a l c i r c u i t s which reduce o r eliminate e r r o r s due to lead
r e s i s t a n c e and t h e r m a l e m f ' s , produce modified v e r s i o n s of the R vs t r e l a t i o n -
ship and provide automatic readout of t h e m e a s u r e m e n t .

F i g u r e 27 i l l u s t r a t e s the r e s i s t a n c e - t e m p e r a t u r e c h a r a c t e r i s t i c s of some
m a t e r i a l s over a broad t e m p e r a t u r e range.

LME C -Memo -68 10 -

52
c

\
I I I I 0
1 \. I I I

0 10 20 30 35 0 200 400 600 IO

TEMPERATURE (OK) TEMPERATURE (OC)

a. AT CRYOGENIC TEMPERATURE b. AT ELEVATED TEMPERATURE
7694-55232
5-2-68

F i g u r e 27. Resistance-Temperature C h a r a c t e r i s t i c s of Some M a t e r i a l s

I
1. Metals

As the t e m p e r a t u r e r i s e s , the r e s i s t a n c e of metallic m a t e r i a l s a l s o r i s e s .

The main f a c t o r causing this r i s e is t h e i n c r e a s e d interaction of e l e c t r o n s with
a t o m s that a r e displaced f r o m t h e i r positions in the metal lattice, resulting in
a s h o r t e r mean f r e e path f o r the e l e c t r o n s . The r i s e in r e s i s t a n c e is r a t h e r
s m a l l and f a i r l y l i n e a r . Values of high t e m p e r a t u r e r e s i s t i v i t i e s of s o m e m e t a l s
may be found in III.F.l of t h i s r e p o r t . All r e s i s t i v i t i e s tend to converge to
-4
values around 1 to 2 x 10 o h m - c m a t high t e m p e r a t u r e s .

R e s i s t a n c e t h e r m o m e t e r s , based on the t e m p e r a t u r e dependence of t h e

r e s i s t i v i t y , a r e widely and i n c r e a s i n g l y used a t lower t e m p e r a t u r e s . In the
r a n g e -183°C to 630°C, indeed, the platinum r e s i s t a n c e t h e r m o m e t e r is the
international standard. Of all m e t a l s , platinum i s the most a p p r o p r i a t e f o r a
r e s i s t a n c e t h e r m o m e t e r b e c a u s e i t is c o m m e r c i a l l y available in p u r e f o r m , it
is e a s i l y workable and is relatively indifferent to its environmental conditions.
In a pure, fully annealed and s t r a i n - f r e e state, it h a s a n R - t relationship which
is especially stable and reproducible.

C o m m e r c i a l r e s i s t a n c e t h e r m o m e t e r s a r e made of copper ( r a n g e -140 to

t 1 2 0 ° C ) , nickel (-180 to t32O"C) o r platinum (-180 to t 5 4 0 " C ) . The r a n g e c a n
b e extended upward (especially for Pt). Careful choice of insulation (high-
s i n t e r e d o r fused alumina) is s a i d to allow the u s e of Pt r e s i s t a n c e t h e r m o -
m e t e r s to t e m p e r a t u r e s not far below t h e melting point (1650°C). Readings a r e
expected to become i r r e p r o d u c i b l e if the s i n t e r i n g point i s reached o r if any
other i r r e v e r s i b l e changes o c c u r in the metal.

F r o m the preceding it is a p p a r e n t t h a t a m e t a l r e s i s t a n c e t h e r m o m e t e r
(using tungsten, for instance) may give s e r v i c e at e x t r e m e l y high t e m p e r a t u r e s ,
however, it may not be the b e s t choice. Dimensional stability i s n e c e s s a r y f o r
its operation, while it s h a r e s with all e l e c t r i c a l methods t h e problems of chemi-
c a l c o r r o s i o n and e l e c t r i c a l insulation. M o r e o v e r , the t e m p e r a t u r e m e a s u r e d
i s a n a v e r a g e over the length of the r e s i s t a n c e , r a t h e r than a point t e m p e r a t u r e .

2. Semiconductors

In semiconductors the t e m p e r a t u r e coefficient of r e s i s t a n c e is usually

negative, and the r a t e of change is g e n e r a l l y much g r e a t e r than in m e t a l s .

LME C -Memo -68 - 10

54
 The effect is due to the g r e a t e r relative n u m b e r s of electrons which a r e p r o -
@ moted into the conduction bands a t higher t e m p e r a t u r e s . The number of con-
ductivity e l e c t r o n s is s m a l l e r than i n the c a s e of m e t a l s (where it is sub-
stantially independent of t e m p e r a t u r e ) and t h e r e f o r e the r e s i s t a n c e , even a t
t h e upper limit of the useful t e m p e r a t u r e range, i s s e v e r a l o r d e r s of magni-
tude higher than i n m e t a l s .

T h e r m i s t o r s a r e semiconductors which can b e brought to a highly r e p r o -

ducible r e s i s t a n c e t e m p e r a t u r e curve. They a r e comparatively insensitive to
impurities. Mixtures of transition m e t a l s (Mn to N i ) oxides with o r without the
addition of spinels (Mg chromite o r aluminate) can b e used. Included in this
category a r e carbon r e s i s t o r s , and doped g e r m a n i u m units, all of which have
the c h a r a c t e r i s t i c of a r e s i s t a n c e d e c r e a s e with i n c r e a s i n g t e m p e r a t u r e s .

However, t h e r m i s t o r s with a positive t e m p e r a t u r e coefficient have a l s o

become available. They exhibit sensitivities up t o t e n t i m e s g r e a t e r than that
of metal r e s i s t a n c e t h e r m o m e t e r s , although their R - t relationship i s f a r m o r e
nonlinear - exponential, in fact. They a r e available i n very s m a l l s i z e s with
rapid t h e r m a l r e s p o n s e ( i n the o r d e r of ms t i m e constants). However, the
v e r y s m a l l t h e r m a l m a s s leads t o problems with nonlinearity of the voltage-
c u r r e n t c h a r a c t e r i s t i c if the measuring c u r r e n t is not limited to values above
2
which I R self-heating of the t h e r m i s t o r element can o c c u r .

T h e s e relatively inexpensive d e v i c e s do not r e q u i r e leadwire r e s i s t a n c e

c o r r e c t i o n s because of t h e i r (usually) high r e s i s t a n c e , and have a l a r g e energy
output p e r d e g r e e t e m p e r a t u r e change a s a favorable r e s u l t of their l a r g e
temperature-resistance coefficient. In o r d e r to cover a wide t e m p e r a t u r e
range, s e v e r a l t h e r m i s t o r s usually a r e required. T h i s i s a n unfavorable con-
sequence of t h e i r high sensitivity and nonlinear R-t c h a r a c t e r i s t i c s , which
c a u s e a given unit t o swing f r o m a n inconveniently low to a n inconveniently
high value if t h e t e m p e r a t u r e span i s too g r e a t .

T h e r m i s t o r s have m o s t commonly been used i n the region -100 to t 3 5 0 ° C ,

but special compositions have g r e a t l y extended t h i s range - a s high a s 1600°C
and a s low a s 4 . 2 " K . T h e i r reputation f o r calibration stability is poor; while
it is t r u e they cannot c o m p a r e i n t h i s r e s p e c t with a platinum r e s i s t a n c e t h e r -
m o m e t e r , they c a n be quite stable when they a r e properly aged before u s e , and
p a r t i c u l a r l y when this u s e is limited to t h e -50 to t1OO"C range.
Q
LMEC-Memo-68-10
55
 Carbon r e s i s t a n c e t h e r m o m e t e r s have been made i n many f o r m s and f r o m
many v a r i e t i e s of n a t u r a l and a r t i f i c i a l c r y s t a l l i n e graphites, and c a r b o n s which
show graphitic p r o p e r t i e s . The c o m m e r c i a l carbon-composition r e s i s t o r , in
s i z e s f r o m 0.1 to 1 watt, 2 t o 150 ohms, exhibits a l a r g e i n c r e a s e of r e s i s t a n c e
i n the neighborhood f r o m 20°K downward. Stock r e s i s t o r s manufactured by the
Allen-Bradley Company w e r e found to be of uniquely high sensitivity and r e p r o -
ducibility. A s e m i - e m p i r i c a l equation developed by Clement applies t o t h e m in
the region below 20°K;

B
- A t T
loglOR loglOR -

w h e r e R is t h e r e s i s t a n c e at t e m p e r a t u r e T , and A, B, and K a r e constants.

When the constants a r e determined by calibration, t e m p e r a t u r e m e a s u r e m e n t s
i n the range 1 to 20°K a r e feasible, with a reproducibility of about 0.2oJ0. At
both helium ( 4 . 2 " K ) and hydrogen ( 2 0 ° K ) temperatures, t h e repeatibility is 0.1%,
even with warming and recooling c y c l e s between observations. About the only
drawbacks connected with carbon r e s i s t a n c e t h e r m o m e t e r s a r e l o s s of sensitiv-
i t y above 20°K and the a d v e r s e influence of rf s t r a y fields on r e s i s t a n c e a t t e m -
p e r a t u r e s much below 4.2"K.

In the t e m p e r a t u r e region below 20°K, and even m o r e so below 4.2"K, re-

producibilities of 0.170 a r e insufficient f o r s o m e purposes. Investigation of
g e r m a n i u m r e s i s t a n c e t h e r m o m e t e r s w a s launched with the intent of providing
a possible future extension of the IPTS t o v e r y low t e m p e r a t u r e s . Both a r s e n i c -
and gallium-doped g e r m a n i u m e l e m e n t s have b e e n fabricated with t h e n e c e s s a r y
precautions to avoid mechanical s t r a i n , contamination, and the effects of s t r a y
resistance. R e p o r t s f r o m various l a b o r a t o r i e s indicate reproducibilities
ranging f r o m 0.0001 to 0.001" a t 4°K. It should b e noted that the f o r m e r figure
approaches the state-of-the-art l i m i t s of m e a s u r e m e n t . N o simple universal
formula is known which approximates the R - t relationship of t h e s e units, s o
that interpolation p r o c e d u r e s a r e somewhat m o r e complex. However, the f a c t
that the t h e r m o m e t e r apparently r e q u i r e s only a single calibration, together
with the availability of high-speed computers, s e r v e s t o minimize this problem.

LME C -Me mo -68 10 -

56
 C o m m e r c i a l g e r m a n i u m units a r e p r e s e n t l y available f r o m s e v e r a l s o u r c e s
to cover the range f r o m about 1 to 40°K. While they undoubtedly will be f u r t h e r
improved, they presently offer solid p e r f o r m a n c e a s e i t h e r supplements to, o r
replacements f o r , o t h e r cryogenic t h e r m o m e t e r s . Investigations of silicon,
gallium a r s e n i d e , and tin oxide elements a r e continuing.

3. H o t - w i r e Techniques

This is a n extension of the r e s i s t a n c e t h e r m o m e t e r . A heated w i r e l o s e s

heat to the surroundings. The r a t e of heat l o s s i s related t o the t e m p e r a t u r e
of the surroundings, and is m e a s u r e d by t h e energy input n e c e s s a r y t o keep the
t e m p e r a t u r e (and r e s i s t a n c e ) of the w i r e constant. Since the w i r e m u s t b e hotter
t h a n the surroundings, it would have to be v e r y hot indeed to be used i n liquid
metal reactors. All mechanical p r o b l e m s applying to the r e s i s t a n c e t h e r m o m e t e r
would thus be aggravated.
0

4. Thin Metallic L a y e r s ( l e s s than 1 0 0 0 A)

T h e s e exhibit r e s i s t i v i t y p r o p e r t i e s similar to those of semiconductors at

liquid hydrogen and helium t e m p e r a t u r e s . Of c o u r s e they a r e not stable at t e m -
p e r a t u r e s at which the vapor p r e s s u r e b e c o m e s appreciable.

5. Oxides

Since the t e m p e r a t u r e coefficient of the r e s i s t i v i t y of s o m e oxides a t v e r y

high t e m p e r a t u r e s is a l s o l a r g e and negative, it i s possible t o conceive of such
high t e m p e r a t u r e "thermistors". T h e r m a l deformation due t o sintering, f r a c -
t u r e due t o t h e r m a l shock, changes in the r e s i s t a n c e due to i m p u r i t i e s and d i s -
locations r e s u l t i n g f r o m r a d i a t i o n damage, and chemical reaction with carbon
a r e t h e a d v e r s e mechanisms which a r e believed t o apply t o such a t e m p e r a t u r e
m e a s u r i n g de vic e.

C. RADIATION PYROMETRY

It i s a n accepted law of nature that all substances at any t e m p e r a t u r e above

absolute z e r o e m i t radiant energy a s a r e s u l t of t h e atomic and m o l e c u l a r agi-
tation t h a t is a s s o c i a t e d with that t e m p e r a t u r e . The r a t e of e m i s s i o n , o r power,
p e r unit area i n c r e a s e s with i n c r e a s i n g t e m p e r a t u r e and m a y be e x p r e s s e d
quantitatively by the following expression:

LME C -Memo -68 10 -

57
 4
W =COT

watts p e r s q u a r e c e n t i m e t e r , if 0, the Stefan-Boltzmann constant, is e x p r e s s e d

i n units of watts p e r s q u a r e centimeter p e r d e g r e e K 4 and T is i n d e g r e e s K.
The dimensionless f a c t o r C , called the t o t a l emissivity o r emittance, is defined
a s the r a t i o of the radiation of the s u r f a c e i n question t o that which would be
emitted by a n otherwise comparable blackbody s u r f a c e at the s a m e t e m p e r a t u r e .

The blackbody s u r f a c e , one which a b s o r b s all incident radiation and r e f l e c t s

none, is a n idealization, but s o m e substances such a s soot and platinum black
do approach unit emissivity v e r y closely. Based on considerations of t h e r m o -
dynamic equilibrium, it i s simple t o demonstrate that a blackbody is a l s o a p e r -
f e c t r a d i a t o r , which a t any t e m p e r a t u r e e m i t s i n each p a r t of the s p e c t r u m the
m a x i m u m energy obtainable p e r unit t i m e f r o m any radiator of equal a r e a , solely
a s a r e s u l t of t e m p e r a t u r e . Both the total intensity and s p e c t r a l distribution of
the emitted energy depend only on the t e m p e r a t u r e of the blackbody radiation;
t h i s f o r m s the b a s i s of the thermodynamic t e m p e r a t u r e s c a l e a t high t e m p e r a t u r e s .

Absolute m e a s u r e m e n t s of radiant power a r e difficult t o make p r e c i s e l y .

However, the m e a s u r e m e n t of the ratio of two radiant powers, s a y E (T ,A)/E
1
( T Z , A) where T is a s t a n d a r d known t e m p e r a t u r e , could s e r v e to define a t e m -
2
p e r a t u r e scale. This p r o c e d u r e w a s followed in establishing the IPTS above the
gold (Au) point.

All c l a s s e s of radiation p y r o m e t e r s (optical, t o t a l radiation and two-color)

a r e valuable i n s t r u m e n t s under any of the following conditions:

1) T e m p e r a t u r e s a r e above the p r a c t i c a l operating range of thermocouples

2) Environments e x i s t which contaminate o r limit the life of thermocouples

3) The t a r g e t s a r e moving o r not e a s i l y a c c e s s i b l e

4) The t a r g e t s would be damaged by contact with p r i m a r y elements like

thermocouples and r e s i s t a n c e t h e r m o m e t e r s

5) It i s d e s i r e d t o m e a s u r e the a v e r a g e t e m p e r a t u r e of l a r g e surface
areas.

F o r f u r t h e r details on radiation p y r o m e t r y s e e Reference 8, pp 69-94.

LME C -Memo -68 - 10

58
 1. Optical
63 a. General

The m e a s u r e m e n t of the radiation f r o m a hot body is the standard method

of measuring high t e m p e r a t u r e . I n m o s t optical p y r o m e t e r s the image of the
hot body as s e e n through a telescope is projected onto the plane of the filament
of an incandescent lamp. An o b s e r v e r matches the brightness of the image
with the brightness of the filament by observing the "disappearance" of the
filament. The l a m p heating c u r r e n t i s then a m e a s u r e of the t e m p e r a t u r e of
the body. Usually f i l t e r s a r e employed to r e s t r i c t the range of light wave-
lengths viewed, and a rotating s e c t o r m e c h a n i s m may be u s e d to reduce the
brightness of the hot body image. The l a m p filament is calibrated against a
blackbody.

F r o m Wien's law:

where J is the b r i g h t n e s s at wavelength X of a blackbody at absolute t e m -

AT
p e r a t u r e T . If the rotating s e c t o r t r a n s m i t s a fraction X of the light f r o m a
s o u r c e at t e m p e r a t u r e T and t h i s is matched in b r i g h t n e s s against the light
2'
f r o m a filament at T a t wavelength A , then:
1

and
C2/XT2
JAT
x=- e
C2/XT1
JAT2 e

so that

With X, X, C2, and T 1 being known, T 2 can be determined.

LMEC -Memo-68 10 -
59
 Neutral g r a y s c r e e n s can b e used instead of rotating s e c t o r s . One of the
big problems i n the u s e of t h i s method is that m o s t m a t e r i a l s a r e not black-
bodies, so that a n emissivity c o r r e c t i o n h a s t o be taken into account. Values
of t h e emissivity a r e not always well known. If the emissivity is independent
of wavelength (a graybody), it is advantageous to c o m p a r e the intensity of
radiation at two wavelengths f r o m the same body by means of a photocell.
Filters o r a monochromator m a y b e used. The r a t i o of intensities a t the two
wavelengths i s a function of the t e m p e r a t u r e (color t e m p e r a t u r e ) .

Thus the optical method f u r n i s h e s a n excellent way of measuring high tem-

peratures. The use of t h i s method in a r e a c t o r r e q u i r e s the provision of a n
optical path f r o m the inside to the outside of the r e a c t o r , collimation of the
light b e a m so that only the d e s i r e d region will be seen, and absorption, con-
tamination and scattering of light by hot carbon vapor and solid p a r t i c l e s of
condensed graphite in the optical path. Light can bebrought out of the i n s t r u -
ment hole and through the p r e s s u r e s h e l l through a tube fitted with m i r r o r s .
It may prove to be more profitable t o c o m p a r e the intensity of emission at two
wavelengths, r a t h e r than t o attempt to m e a s u r e the total e m i s s i o n of light.
The two wavelengths method r e d u c e s absorption by carbon vapor and CN to a
0 0

minimum. The carbon a r c s p e c t r u m suggests that 4900 A and 6800 A would be

a c c e ptable wave1engths .

A novel method of optical p y r o m e t r y h a s been developed by the Linde Air

P r o d u c t s Company. It is intended f o r inaccessible regions. A light path is
provided f o r emitted light by m e a n s of a sapphire (fused aluminum oxide) light
guide. The light guide consists of a monocrystalline rod which can be bent to
f i t the g e o m e t r y of the design. The rod is f i r e polished and can presumably be
passed through a p r e s s u r e s e a l . O r d i n a r y rod lengths a r e up to 18 i n . , but
l a r g e r lengths can b e fabricated on o r d e r . Thicknesses of the r o d s c a n b e up
t o 1 / 4 in.

Artificial sapphire is c o l o r l e s s and has b e t t e r light t r a n s m i s s i o n than

lucite. Its melting point is about 2 0 0 0 ° C . At 1500°C, it i s v e r y r e s i s t a n t t o
chemical attack, though silicon produces a haze effect on the s u r f a c e a f t e r long
exposure (months). Thermal-shock r e s i s t a n c e is reported t o be sufficiently
good to allow fire-polishing with a naked hydrocarbon-oxygen flame. Both a b s o -
lute brightness and color t e m p e r a t u r e c a n be m e a s u r e d . The light c a n a l s o be
directed t o a thermopile.
LME C -Memo -68 - 10
60
b. Polychromatic Pyrometry

Another method worthy of consideration with r e s p e c t to p r a c t i c a l t e m p e r a -

t u r e m e a s u r e m e n t s utilizes color, o r polychromatic, p y r o m e t r y . The color
temperature T of a non-blackbody may be defined a s the t e m p e r a t u r e a t which
C
it i s n e c e s s a r y t o o p e r a t e a blackbody so that i t s radiation will m a t c h the visual
color of the s o u r c e being studied. In p a r t i c u l a r , if we choose two wavelengths
(colors), h > A,, i n the 0.4 t o 0.7 p range, we can m e a s u r e a T c by taking the
ratio of powers radiated f r o m a n incandescent body at the wavelengths X 1 andX2.
It may b e shown that, in this situation:

where 2 and E 1 a r e the e m i s s i v i t i e s at the wavelengths % and X 1' respectively.

F o r both the blackbody and graybody, I n < / < vanishes and T = Tc. F o r m o s t
1 2
common materials, emissivity is a slowly decreasing function of wavelength in
the visual s p e c t r u m . This m e a n s that the r a t i o E l/c is g r e a t e r than, and not
g r e a t l y different f r o m , unity. Thus, T is usually higher than, but not g r e a t l y
C
different f r o m , T. As an example, f o r tungsten, T i s 8 to 24°C higher than T
C
in the range 8 0 0 t o 1500°C. ( F o r h2 -0.65p, A, -0.5p.) In the s a m e range,
T v a r i e s f r o m 41 to a s much a s 123" lower than T. I t must be realized, how-
B
e v e r , that f o r some important m a t e r i a l s , T > Tc a n d / o r ( T - Tc) > (T TB). -
T h e r e a r e a number of both l a b o r a t o r y and c o m m e r c i a l models of two-color
o r ratio p y r o m e t e r s . They all f e a t u r e optical and electronic s y s t e m s of s o m e
complexity, but with the advantages of d i r e c t (often l i n e a r ) read-out and high
sensitivity. Some experimental i n s t r u m e n t s have been constructed operating
with t h r e e o r m o r e c o l o r s , thus requiring t h e m e a s u r e m e n t of multiple ratios.
This scheme, along with that of shifting A, and A, to other regions of the spec-
t r u m (such a s t h e i n f r a r e d ) , h a s a s i t s p u r p o s e the reduction of e r r o r s c a u s e d
by e x c e s s i v e o r anomalous e m i s s i v i t y variation with wavelength.

Total o r panchromatic, radiation p y r o m e t r y is yet another method. Because

of its n a t u r e and underlying principles, the radiation p y r o m e t e r ("totaltt will be
understood) is t h e s i m p l e s t t o d e s c r i b e and perhaps the e a s i e s t to u s e and u n d e r -
stand, but potentially the l e a s t a c c u r a t e . As h a s been shown, it i s possible t o

LMEC-Memo-68 - 10
61
m e a s u r e t h e t e m p e r a t u r e of a s o u r c e by m e a s u r i n g its radiant power output
over some v e r y l a r g e s p e c t r a l range. T h i s m a y be done by focusing the emitted
radiation on a n absorbing a r e a , called the r e c e i v e r , by m e a n s of a l e n s o r m i r -
r o r system. T h e t e m p e r a t u r e of the r e c e i v e r r i s e s until its own r a t e of heat
l o s s is equal to its r a t e of absorption. T h i s equilibrium t e m p e r a t u r e is seldom
m o r e than 30 to 4 0 ° C higher than t h e ambient, even f o r a v e r y intense s o u r c e .
The significant f a c t is that, a f t e r equilibrium has been reached, a change in
t e m p e r a t u r e of the s o u r c e will produce a change in t h e t e m p e r a t u r e of t h e r e -
c e i v e r , albeit a much s m a l l e r one, through the medium of the emitted radiation.

T h e r e a r e s e v e r a l s c h e m e s f o r transducing the t e m p e r a t u r e information of

the r e c e i v e r . Most commonly, a sensitive thermocouple o r t h e r m o p i l e i s con-
nected t o t h e s m a l l blackened m e t a l l i c d i s c acting a s a r e c e i v e r , and the t e m -
p e r a t u r e changes a r e m e a s u r e d by the g e n e r a t e d emf. The r e c e i v e r c a n be a
s t r i p of blackened platinum o r semiconducting m a t e r i a l forming one a r m of a
r e s i s t a n c e b r i d g e , i. e . , a b o l o m e t e r . T h e r e a r e occasions when the r e c e i v e r
i s a bimetallic s p i r a l actuating a p o i n t e r , o r a capsule in which g a s p r e s s u r e
changes with t e m p e r a t u r e .

Speaking in m o r e g e n e r a l t e r m s , t h e r e is no need f o r the s o u r c e power t o

be t r a n s l a t e d into t h e r m a l changes at all. Photosensitive d e t e c t o r s m a y be used
to respond to the d i r e c t radiation impinging upon them. T h i s c l a s s of device
will have a much s h o r t e r r e s p o n s e t i m e and potentially higher sensitivity, but
the l a t t e r v a r i e s widely with wavelength. In fact, the bandwidth of photosensitive
d e t e c t o r s c l a s s i f i e s t h e m somewhere between the narrow-band optical and c o l o r
p y r o m e t e r s and the wide-band t h e r m a l radiation p y r o m e t e r s . F o r this reason,
t h e s e i n s t r u m e n t s a r e s o m e t i m e s called p a r t i a l - r a d i a t i o n p y r o m e t e r s . At any
r a t e , t h e t h e r m o e l e c t r i c radiation units a r e t h e m o s t widely used i n t h e i r c l a s s
and have the advantages of ruggedness, relative immunity f r o m damage by high
ambient t e m p e r a t u r e and the aforementioned sensitivity over wide wavelength
ranges.

2. E m i s s i o n Spectroscopy

A typical example of e m i s s i o n s p e c t r o s c o p y involves the m e a s u r e m e n t of

the r e l a t i v e intensity of s p e c t r a l l i n e s emitted in the optical and ultraviolet
region by a radiating s p e c i e s of the g a s o r p l a s m a . Using Boltzmann s t a t i s t i c s

LMEC -Memo -68 10 -

62
 and t h e theory of a t o m i c s p e c t r a , the r e l a t i v e intensity of two s p e c t r a l lines
@ f r o m t h e s a m e e l e m e n t is I - kl exp ( k Z / T ) w h e r e k 1 is a constant involving
R -
the s t a t i s t i c a l weights, t r a n s i t i o n probabilities, and f r e q u e n c i e s of the lines
and k is a constant proportional t o the differences in e n e r g y levels LE of the
2
s t a t e s r e p r e s e n t e d by the l i n e s . A plot of In IR v s 1 / T will give a s t r a i g h t line
of slope k2; T may be m e a s u r e d by determination of I k l and k2. Sensitivity
R’
of the m e a s u r e m e n t will depend on t h e value of k all other things being equal.
2’
It is t h e r e f o r e n e c e s s a r y to s e l e c t two l i n e s w h e r e LE is l a r g e , but still within
the wavelength span of the s p e c t r o g r a p h , and a l s o within the intensity span that
c a n b e accommodated by the film emulsion and d e n s i t o m e t e r on a single e x p o s u r e .
Sometimes the d i r e c t method is prohibited by lack of a suitable s p e c t r u m , o r f o r
other r e a s o n s . In this event, t h e r e a r e the i n d i r e c t determinations b a s e d o n
m e a s u r e m e n t s of Doppler o r S t a r k effect broadening of s p e c t r a l l i n e s , of cyclo-
t r o n radiation, and using probe techniques - employing microwaves, thermal
n e u t r o n s o r magnetic s e a r c h coils.

3. I n f r a r e d Photography

Where r e l a t i v e t e m p e r a t u r e information o v e r a broad expanse of a r e a i s

d e s i r e d , s u c h a s the t e m p e r a t u r e gradations in a multitube r a d i a t o r , a photo-
graphic technique c a n prove to be s i m p l e r , f a s t e r , l e s s expensive and m o r e
informative than a n u m b e r of thermocouples.

To obtain t e m p e r a t u r e d a t a m o r e e a s i l y , viewing p o r t s w e r e installed i n

the h e a t sink of one such r a d i a t o r so t h a t it could be observed during o p e r a t i o n .
0

Photographs w e r e t a k e n of t h e r a d i a t o r using 9000 A P o l a r o i d i n f r a r e d - s e n s i t i v e

film. R e s u l t s indicate that substantial temperature differences existing within
the r a d i a t o r unit w e r e e a s i l y seen, and that liquid collecting at t h e d i s c h a r g e
end of the r a d i a t o r was detected by t e m p e r a t u r e m e a s u r e m e n t . Where t h e r e
w a s no evidence of any substantial t e m p e r a t u r e change along o r a c r o s s the
t u b e s , it w a s concluded that liquid had not accumulated i n the tubes o r h e a d e r s .
But w h e r e the liquid h e a d e r s w e r e no longer visible in the f i l m , t h i s w a s taken
a s a n indication that a substantial reduction in t e m p e r a t u r e had o c c u r r e d along
the tube. In one c a s e a t e m p e r a t u r e d r o p of approximately 1 2 5 ° F o c c u r r e d
a c r o s s the indicated s h a r p color change.

LME C -Memo 6 8 10 - -
63
 With t h e use of r e f e r e n c e thermocouples and c a r e f u l control of f i l m ex-
p o s u r e t i m e s , a color vs t e m p e r a t u r e g r a d i e n t relationship c a n be established. @
D. THERMAL EXPANSION OF MATERIALS

1. Liquid T h e r m o m e t e r s

a. General. P r o b a b l y t h e most widely used t e m p e r a t u r e m e a s u r i n g device in

both science and industry is the liquid-in-glass t h e r m o m e t e r . T h i s i n s t r u m e n t ,
filled with a liquid s u c h a s m e r c u r y , toluene, alcohol, o r pentane, depends f o r
its operation on the relatively l a r g e t e m p e r a t u r e -dependent volume expansion
of the liquid and the much s m a l l e r expansion of the g l a s s c o n t a i n e r . The m e r -
c u r y unit c a n be used f r o m -38°C (its f r e e z i n g point) to about 6OO0C. T h i s
l a t t e r t e m p e r a t u r e is w e l l above the boiling point of m e r c u r y , s o a n i n e r t g a s
at positive p r e s s u r e m u s t be used as a f i l l e r . Furthermore, special glasses
with high softening t e m p e r a t u r e s a r e r e q u i r e d f o r such m e a s u r e m e n t s . To
extend the low t e m p e r a t u r e r a n g e downwards, the other liquids come into u s e ;
some pentane thermometers have been used down to - 1 9 6 ° C .

Because of the generally small c r o s s - s e c t i o n and s h o r t scale-length of the

c a p i l l a r y column, v a r i o u s a r t i f i c e s have had t o be developed to overcome r e a d -
ing difficulties in the liquid-in-glass t h e r m o m e t e r s . Coloring agents in the
liquid o r i n the c a p i l l a r y tubing, magnification of the liquid column by a l e n s -
like g l a s s tubing, and minimizing of g l a r e and reflection, have all proved to be
effective. Another difficulty, s e p a r a t i o n of the liquid column into two o r m o r e
p a r t s , c a n usually be t a k e n c a r e of by p r o p e r manipulation.

Some t h e r m o m e t e r s a r e designed to r e a d c o r r e c t l y only when the bulb and

e n t i r e liquid-filled s t e m a r e exposed to the environment to be m e a s u r e d ; o t h e r s
r e q u i r e only t h e bulb and a s h o r t length of the s t e m to be i m m e r s e d . Because
t h e l a t t e r , o r p a r t i a l - i m m e r s i o n t y p e s , a r e often used with s t e m t e m p e r a t u r e s
g r e a t l y different than bulb t e m p e r a t u r e s , they a r e not as a c c u r a t e as the total-
i m m e r s i o n t h e r m o m e t e rs . E m e r g ent - s t e m c o r r e c t i o n s a r e often d e t e r m i n e d
f o r t o t a l - i m m e r s i o n units used at p a r t i a l i m m e r s i o n .

b. Differential M e a s u r e m e n t s . T h e r e a r e many a r e a s of t e m p e r a t u r e m e a s u r e -
ment w h e r e t h e a c c u r a c y at any one t e m p e r a t u r e is not as important a s t h e a c -
c u r a c y of the t e m p e r a t u r e i n t e r v a l . Beckmann and c a l o r i m e t r i c t h e r m o m e t e r s

LME C -Memo -6 8 - 10
64
a r e constructed so a s to provide a c c u r a t e differential m e a s u r e m e n t s i n various
different t e m p e r a t u r e ranges by addition o r removal of portions of the liquid
from the bulb. Granting that these units a r e m o r e expensive and complex than
o t h e r s of t h e i r c l a s s , it i s s t i l l safe t o s a y that liquid-in-glass t h e r m o m e t e r s
owe t h e i r popularity to low c o s t , simplicity, high reliability, and long life ( a s -
suming accidental b r e a k a g e to b e the exception r a t h e r than the r u l e ) .

2. Gas T h e r m o m e t r y

It i s possible to m e a s u r e : ( 1 ) the volume change of a permanent g a s a t

constant p r e s s u r e ; (2) the p r e s s u r e change of a permanent gas a t constant
volume; and ( 3 ) change of vapor p r e s s u r e in p r e s e n c e of the condensed phase.
Method 3 i s especially sensitive, but the t e m p e r a t u r e r a n g e f o r any given
t h e r m o m e t r i c sub stance i s correspondingly limited.

In the high t e m p e r a t u r e range and a t the p r e s s u r e s encountered in r e a c t o r s ,

the ideal g a s law will be f a i r l y a c c u r a t e f o r permanent g a s e s , s o that the r e a d -
ings in methods 1 and 2 will be proportional to the absolute t e m p e r a t u r e ' i n a c -
cordance with the G e n e r a l Gas Law:

-
PV = constant

In method 3 the vapor p r e s s u r e P is related to the absolute t e m p e r a t u r e T

by the equation

log P = A
B
--
T

w h e r e A and B a r e specific constants f o r each m a t e r i a l .

In principle, g a s t h e r m o m e t r y c a n b e used a t a l l t e m p e r a t u r e s . However,

a t high t e m p e r a t u r e s t h e r e a r e g r e a t p r a c t i c a l difficulties. First, the gas has
to be contained i n a strong, rigid, gas-tight container, t h e r e a r e no m a t e r i a l s
which would fulfill t h e s e conditions at t e m p e r a t u r e s of the o r d e r of 2500°K.
Second, a gas t h e r m o m e t e r m e a s u r e s t e m p e r a t u r e o v e r the e n t i r e volume of
the gas. In methods 1 and 2, the a v e r a g e t e m p e r a t u r e of the g a s i s m e a s u r e d ;
method 3 m e a s u r e s (under equilibrium conditions) the t e m p e r a t u r e of the liquid-
gas interface. If the proposed device is to m e a s u r e the t e m p e r a t u r e of a s m a l l

LMEC-Memo -68 - 10
65
region, the g a s volume m u s t b e kept very small. In r e a c t o r s , this m e a n s that
the e n t i r e gas volume must be deep inside the r e a c t o r giving r i s e t o the p r o b l e m
of how t o get the signal out.

In method 1 a movable manostat, such a s a piston, is needed. A gas-tight

piston could b e connected rigidly t o a recording device in the cool region. If a
piston w e r e to move at least 1 mm p e r 100°K i n the 2500°K range, the t o t a l
volume of gas i s of the o r d e r of 1 rnl, so that a 100°K r i s e i n t h e t e m p e r a t u r e
m e a n s a volume i n c r e a s e of 0.04 ml. The a r e a of t h e piston head is then at
m o s t 0.4 c m
2
. T h i s a p p e a r s feasible. The question of a gas-tight container
and a gas-tight f i t between piston and container is, however, m o r e difficult. It
can be safely predicted t h a t if a tight f i t is indeed achieved at low t e m p e r a t u r e s ,
t h e piston and b a r r e l will s i n t e r together when high t e m p e r a t u r e s a r e reached.
Therefore, method 1 a p p e a r s to be i m p r a c t i c a l . Methods 2 and 3 depend on t h e
de ve lop me nt of a hi g h - t empe r a t u r e p r e s s u r e t r a n sduc e r .
3. Bimetals

A b i m e t a l t h e r m o m e t e r t a k e s advantage of the differential expansion of two

solids. If the solids a r e two joined s t r i p s , c u r v a t u r e will r e s u l t which can be
readily m e a s u r e d . Readings will be reproducible only if t h e e l a s t i c limit of the
m a t e r i a l s is not exceeded, s o that t h e r e is l i t t l e o r no mechanical h y s t e r e s i s .
This is a condition which is difficult t o fulfill at high t e m p e r a t u r e s , a t which
elasticity ol; metals is v e r y low. Sagging and multiple bending a r e to be expected.

Operation to as high a s 5 0 0 ° C is feasible using a high nickel-content invar

v s a nickel-chromium-iron alloy. At t e m p e r a t u r e s below - 1 00" C, sensitivity
d r o p s off rapidly b e c a u s e the coefficients of expansion of the m e t a l s approach
each other. Bimetal t h e r m o m e t e r s have many advantages; they a r e available
in both s h o r t and long t e m p e r a t u r e spans; they usually can be over-ranged with-
out h a r m ; they will retain t h e i r a c c u r a c y (as high as 1/2%) indefinitely if handled
with reasonable c a r e , and a r e e a s y t o r e s e t if recalibration i s n e c e s s a r y ; they
a r e e a s i e r to read, l e s s subject t o breakage and do not r e q u i r e s t e m c o r r e c t i o n s ,
as compared with liquid-in-glass t h e r m o m e t e r s . If the s t r i p i s coiled into a
helix o r s p i r a l , then t e m p e r a t u r e changes will produce a change in the c u r v a t u r e
of the s t r i p . As long a s the s t r a i n thus produced does not exceed the elastic
l i m i t s of the m e t a l s , the change in c u r v a t u r e c a n be t r a n s l a t e d into an angular

LME C -Memo 68 - 10 -
66
a deflection, d i r e c t l y and reproducibly proportional to the t e m p e r a t u r e change.
Obviously, the m a t e r i a l s involved in the bimetal element a r e v e r y important.

4. Filled-Svstem T h e r m o m e t e r s

F i l l e d - s y s t e m t h e r m o m e t e r s , using temperature-induced liquid o r g a s

expansion effects, a r e made up of four c l a s s e s , according to filled m a t e r i a l .
The Scientific Apparatus Manufacturer’s As sociation h a s established C l a s s I,
liquid-filled; C l a s s 11, vapor p r e s s u r e ( p a r t i a l filling of a volatile liquid);
C l a s s 111, gas-filled; and C l a s s V, mercury-filled. T h e r e is no Class I V ,
and C l a s s V i s a special c a s e of C l a s s I. All c l a s s e s a r e somewhat s i m i l a r
i n appearance, construction and operation. They make common u s e of a bulb,
a connecting capillary and a mechanism, usually a bourdon tube, which r e -
sponds to changes i n p r e s s u r e o r volume of t h e filling fluid. The bourdon is
mounted in a c a s e with a mechanical linkage to a pointer o r pen to provide
read-out on a suitable s c a l e o r c h a r t . Some s y s t e m s incorporate a compensating
c a p i l l a r y and bourdon tube to c o r r e c t f o r ambient changes along the capillary
and at the c a s e . Choice of a p a r t i c u l a r c l a s s depends on the application involved.
F a c t o r s t o be considered include m a x i m u m and m i n i m u m t e m p e r a t u r e s , s i z e of
t e m p e r a t u r e span d e s i r e d , speed and linearity of r e s p o n s e , sensitivity, a c c u r a c y
and cost. As an example, the m o s t common s y s t e m , the C l a s s I, i s usually
filled with a n inert hydrocarbon, g e n e r a l l y p e r m i t s small bulb s i z e , uniform
scale graduation and spans a s n a r r o w as 10°C (but only a t the expense of small
bulb s i z e , since the two a r e inversely r e l a t e d ) . C l a s s I s y s t e m s a r e usually
r e s t r i c t e d to operation in a t e m p e r a t u r e range of -80°C to 25OoC, not as wide
a range as C l a s s e s I11 and V. They r e q u i r e compensation, unlike C l a s s II, but
this can be done f a i r l y accurately. They a r e n o t a s low-cost o r a s fast-responding
a s C l a s s 11. F r o m these c o m p a r i s o n s , one c a n see the importance of application
r e q u i r e m e n t s t o the choice of f i l l e d s y s t e m t h e r m o m e t e r s .

E. VARIATIONS IN DLELECTRIC CONSTANTS

The d i e l e c t r i c constants of i n s u l a t o r s show a m a r k e d t e m p e r a t u r e dependence,

since the orientation polarization, which is due to the dipole moment of the
molecule, is inversely proportional t o the t e m p e r a t u r e :

LME C -Memo -68 1 0 -

67
 Po = 41TN/3 (p2/3kT)

where

D = d i e l e c t r i c constant,

p = density,

M = molecular weight,

PD = distortion polarization,

Po = orientation polarization,
N = Avogadro's number,

p = dipole moment,

k = Boltzmann's constant, and

T = absolute t e m p e r a t u r e .

This method h a s been used f o r measuring t e m p e r a t u r e s , but is especially

applicable t o m a t e r i a l s of high dipole moment a t low t e m p e r a t u r e s . At high
temperatures P b e c o m e s relatively insignificant compared with P,,; moreover,
0
m o s t insulators fail and become conductors.

F. THERMIONIC EMISSION

The thermionic e m i s s i o n c u r r e n t f r o m the s u r f a c e of a hot metal i s highly

temperature-dependent:

2 -B/T
I=AT e

One advantage is that the e l e c t r i c a l signal is built in. Unfortunately, how-

e v e r , the method r e q u i r e s a good vacuum and this cannot be attained i n a n a l l -
hot s y s t e m . In the p r e s e n c e of appreciable quantities of v a p o r s , the emitting
s u r f a c e is poisoned and the e l e c t r o n path is no longer collision-free.

LME C -Memo -68 - 10

68
n G. ACOUSTIC METHODS
63 1. Velocity of Sound in Gas

The velocity of sound, w, i n a perfect g a s is r e l a t e d t o the Kelvin t e m -

p e r a t u r e T by w2 = ( y R / M ) T w h e r e y is t h e specific heat ratio, R the u n i v e r s a l
g a s constant, and M the molecular weight of the g a s .

A typical experimental realization of this equation makes u s e of two t r a n s -

d u c e r s , spaced at a known distance, with c i r c u i t r y f o r continuously measuring
the delay t i m e of a n ultrasonic wave generated by one t r a n s d u c e r and received
by t h e o t h e r . This technique thus r e d u c e s t e m p e r a t u r e m e a s u r e m e n t t o a t i m e
m e a s u r e m e n t , a great advantage b e c a u s e of the high a c c u r a c y with which t h e
l a t t e r p a r a m e t e r may be determined. In addition, b e c a u s e t h e g a s itself is the
t h e r m o m e t e r element, v e r y rapid t e m p e r a t u r e changes may be followed, and
e r r o r s normally introduced by t h e r m o m e t e r e l e m e n t s (heat l e a k s , t h e r m a l l a g s ,
e t c . ) a r e absent. Of c o u r s e t h e r e a r e the attendant difficulties: d e p a r t u r e of
the g a s f r o m ideality; the n e c e s s i t y f o r a c c u r a t e l y determining y ; t h e dependence
of w on p r e s s u r e , which m u s t t h e r e f o r e be c o r r e c t e d ; and the f a c t that instead
of m e a s u r i n g point t e m p e r a t u r e , a n a v e r a g e t e m p e r a t u r e over the path is being
det e r mined.

2. -
F r e qu enc y Change ( 9)

A single t r a n s d u c e r - p r o b e p e n e t r a t e s a f u r n a c e , terminating i n a f r e e end.

Standing waves a r e established in the probe by the attached t r a n s d u c e r , the
wavelength p r e d e t e r m i n e d by the length and m a t e r i a l of the probe. Attached to
t h e t r a n s d u c e r i s a sensing c r y s t a l , the output voltage f r o m which is fed into a
power a m p l i f i e r , thus producing sinusoidal oscillatory energy b y the principle
of e l e c t r i c a l feedback. T h e output impedance of the a m p l i f i e r is p r o p e r l y
matched to t h e impedance of the t r a n s d u c e r to s e c u r e maximum power t r a n s f e r .

With the amplifier operating, any random disturbance in e i t h e r t h e acoustic

o r the electronic s y s t e m produces a t r a n s i e n t output voltage f r o m the c r y s t a l ,
which, amplified and applied t o the t r a n s d u c e r , i n t u r n excites t h e c r y s t a l a t
higher amplitude. Since those vibrations which a r e at the resonant frequency
of t h e acoustic s y s t e m will b e strongest, vibration of the s y s t e m will theoreti-
cally be sustained a t the resonant frequency.
n

LME C -Memo -68 10 -

69
3. Phase-Relation ( 9 )
w
A

Two coupler rods a r e attached t o a t r a n s d u c e r . One of the rods i s e n -

closed, f o r p a r t of its length, i n a r e s i s t a n c e furnace; the other i s at a f i x e d
temperature. Both r o d s t e r m i n a t e in acoustically perfect loads. If the two
t r a n s m i s s i o n lines a r e identical and if both a r e maintained at identical t e m -
p e r a t u r e , traveling waves i n e a c h will b e in phase a t points equidistant f r o m
the point of attachment to the common coupler. If a m e a s u r e d section, 1, of
one of the lines is heated, the velocity of sound in t h i s section will d e c r e a s e ,
resulting i n a change i n phase between the heated section and the load.

The phase angle between the two traveling waves is given by the relation:

where
q = p h a s e angle between t h e traveling wave ( r a d i a n s ) ,

f = driving frequency (kcps),

1 = length of heated section ( c m ) ,

c = velocity of sound in t h e heated section ( c m / s e c ) , and

c = velocity of sound in t h e unheated section ( c m l s e c ) .

0

If the phase difference between the signals f r o m two sensing c r y s t a l s c a n

be m e a s u r e d by means of a phase detector, variation in the t e m p e r a t u r e of the
heated section c a n b e calculated f r o m the variation i n the phase angle.

4. SparkGap

Another m e c h a n i s m u s e s two s p a r k gaps. The sonic wave f r o m a s p a r k

a c r o s s the first gap introduces a discontinuity in a d i s c h a r g e a c r o s s the second.
The propagation t i m e f o r the wave to t r a v e l the intervening s p a c e thereby p r o -
vides a m e a s u r e of the t e m p e r a t u r e of that space. This method may b e r e n d e r e d
i m p r a c t i c a l by the p r e s e n c e of ionizing radiation. Charge leakage a c r o s s the
s p a r k gap and its leads would probably r e n d e r it inoperative. The usual high
t e m p e r a t u r e insulation and dimensional problems a r e a l s o expected.

LMEC-Memo -68 - 10
70
 The amount of charge leakage naturally depends on t h e voltage applied and
the intensity of the radiation. At high enough voltage (1000 v) and intensities it
i s possible to get a t o t a l discharge when a g a m m a r a y p a s s e s through the s p a r k
gap, a n effect similar to that observed i n a s p a r k d i s c h a r g e counter.

H. THERMOCHEMICAL

These techniques depend on m e a s u r i n g an equilibrium o r reaction r a t e , t h e

t e m p e r a t u r e dependence of which i s known. The number of reactions which
have been investigated at v e r y high t e m p e r a t u r e s is s m a l l ; mostly they a r e gas
reactions; f o r example, the reaction N t Oz = 2 N 0 . Reference 3, Section 2.5,
2
d i s c u s s e s this method i n g r e a t e r detail.

I. FIXED POINT

By t h e i r n a t u r e , t h e s e methods m e a s u r e only one t e m p e r a t u r e , the one at

which the phase change o c c u r s . Although this m a k e s t h e m unsuitable f o r a
continuous t e m p e r a t u r e - m e a s u r i n g device, the possibility of using a fixed point
as an indicator of undue o r c a t a s t r o p i c t e m p e r a t u r e r i s e should not be ignored.
Such a device could b e made v e r y simple t o s e r v e as a n alarm. It may consist
of a w i r e of a r b i t r a r y high melting point, which completes a n e l e c t r i c a l c i r c u i t .
The leads can be rods of a v e r y high-melting m a t e r i a l such a s zirconium c a r -
bide o r tantalum carbide. For high t e m p e r a t u r e , the w i r e could be a tungsten-
molybdenum alloy. Tungsten and molybdenum f o r m a continuous s e r i e s of solid
solutions, with melting points varying continuously f r o m 2620 to 338OoC, and
the d e s i r e d f a i l u r e point c a n be chosen anywhere in this range.

P r a c t i c a l p r o b l e m s f o r such a device r e s e m b l e those encountered in a

thermocouple assembly: the leads m u s t b e prevented f r o m shorting and the
w i r e m u s t be protected f r o m chemical change. It is possible that shorting
could be avoided by inserting the l e a d s through two adjacent i n s t r u m e n t holes
and passing the w i r e between the holes horizontally. The second condition is
m o r e difficult. Carburization of tungsten and molybdenum leads to t h e f o r -
mation of lower-melting eutectics. If a c a r b i d e i s used, the melting point may
still be changed by the absorption of carbon. F o r instance, TaC (melting point
3800°C) f o r m s a eutectic with c a r b o n (10% C b y weight) with a melting point of
3300°C. I f , on the other hand, a eutectic composition i s used, deviation f r o m

LMEC -Memo -68 10 -

71
the initial composition will r e s u l t i n a r a i s i n g of the liquidus point. However,
some liquid phase will always f o r m at the melting point of the eutectic, and it @
is probable that c i r c u i t f a i l u r e will r e s u l t . A method m u s t a l s o be found to
prevent a spurious signal f r o m being produced by shorting through the body of
the reactor.

J. PHOSPHOR LUMINESCENCE

This method utilizes the d e c r e a s e of luminescent efficiency of a phosphor

with i n c r e a s i n g t e m p e r a t u r e . T h i s is a v e r y sensitive technique since the
efficiency may d e c r e a s e by s e v e r a l p e r c e n t p e r O C. F o r instance, a ZnS-CdS
phosphor d e c r e a s e s i n efficiency by a f a c t o r of 1 0 0 when heated f r o m 5 t o 4 0 ° C .
T h i s method h a s no known high t e m p e r a t u r e applications b e c a u s e of m a t e r i a l
difficulties.

K. NOISE GENERATED IN ELECTRICAL ELEMENTS

Noise in a n e l e c t r i c a l c i r c u i t can b e reduced only t o a finite lower limit.

At this limit the r e s i d u a l noise (Johnson noise) is due t o t h e random uneven-
n e s s e s in e l e c t r o n distribution, a phenomenon analogous t o t h e Brownian motion.
The uneven distribution g i v e s r i s e to a small voltage. While the t i m e a v e r a g e
of t h e voltage is z e r o ( b e c a u s e displacement i s equally likely in all d i r e c t i o n s ) ,
t h e t i m e a v e r a g e of the s q u a r e of t h e voltage i s not, and is given by the Nyquist
e quat ion:

d (p2 ) = 4kT R e [ Z ( f ) ] df

where
R e [ Z ( f ) ] = the r e a l p a r t of the complex impedance Z(f), a function of the
frequency f ,

k = Boltzmann's constant ( R / N0),

T = the absolute t e m p e r a t u r e , and

d(V2) = t h e contribution to V2 of the frequency range of width df at f .

T h e total n o i s e is obtained by integrating over the f r e q u e n c y range.

LMEC-Memo-68-10
72
 When two c i r c u i t s consisting of a p a r a l l e l combination of a r e s i s t a n c e and
6d a capacitance a r e equated, it can be shown that the r a t i o of the integrals

i s equal to the r a t i o s of the r e s i s t a n c e s . Thus, if the noise levels in the two

c i r c u i t s a r e equal, the t e m p e r a t u r e s of the two r e s i s t o r s a r e i n v e r s e l y p r o -
portional t o t h e i r r e s i s t a n c e s .

In s u c h a n instrument, the r e s i s t o r i s typically a platinum w i r e welded t o

platinum leads, and shielded by a platinum sheet. T h e r e a p p e a r s t o b e no
reason, however, why a higher melting metal could not be used.

The u s e of t h i s i n s t r u m e n t depends, of c o u r s e , on the elimination of a l l

p a r a s i t i c voltages and s o u r c e s of nonrandom noise. T h e r m o e l e c t r i c junctions,
grid c u r r e n t s , and net thermionic e m i s s i o n must be eliminated. In the p r e s e n t
c a s e , considerable interference may be expected due to radiation effects. Since
electron displacements due t o g a m m a - r a d i a t i o n a r e l a r g e , it would s e e m that
even a m o d e r a t e dose r a t e would have a disproportionately g r e a t effect on the
a v e r a g e of the s q u a r e s of the displacements. The dose r a t e dependence of the
noise could be obtained theoretically, so that the use of the noise t h e r m o m e t e r
cannot b e eliminated on this b a s i s alone.

A c c u r a c i e s obtained under l a b o r a t o r y conditions a r e of the o r d e r of 0.3 to

0.570 a t 7 0 0 ° C . Response t i m e i s not good, a s a t i m e of the o r d e r of 500 s e c i s
r e q u i r e d to attain good balance.

Even under optimum conditions, use of this method r e q u i r e s the i n s e r t i o n

of a r e s i s t o r w i r e with shielding of the s a m e m a t e r i a l into t h e i n s t r u m e n t hole.
The r e s i s t a n c e m u s t s t a y constant. Thus the noise method i s not expected t o
be completely satisfactory.

L. DIFFUSION

The diffusion of g a s e s through o r i f i c e s and the diffusion of solutes through

s e m i - p o r o u s m e m b r a n e s a r e both t e m p e r a t u r e dependent. F o r high t e m p e r a -
t u r e s , the f o r m e r method i s the one that i s applicable.

LMEC -Memo -68 -1 0

73
 The number of molecules of a n i d e a l g a s hitting a s u r f a c e of a r e a dA p e r
s e c is:

dn= -
3 iipdA
13

w h e r e ii is the root mean s q u a r e velocity and p the n mber of moleci l e s p e r

unit volume.

Substituting U = d T / M p and p = P N o / R T ,

lPN o, / 3 m d A
dn = 13

where
N = Avogadro's n u m b e r ,
0

P = the p r e s s u r e ,
R = the g a s constant,

T = the absolute t e m p e r a t u r e , and

M = the m o l e c u l a r weight.

T h u s , at constant p r e s s u r e ? dn is i n v e r s e l y proportional t o the s q u a r e root of

the t e m p e r a t u r e .

A t e m p e r a t u r e probe utilizing the diffusion principle m a y be c o n s t r u c t e d

a s follows: a long U-tube of a high melting m a t e r i a l such a s tungsten would be
i n s e r t e d into the r e a c t o r . At the point at which the t e m p e r a t u r e is to be m e a -
s u r e d ? a p a r t i t i o n is placed a c r o s s the tube and a diffusion pinhole is made in
the partition. The g a s p r e s s u r e i s maintained at a constant l e v e l on one side
of t h e partition and is pumped down to a n e a r - z e r o value on the other side.
The steady-state volume of air pumped through the p a r t i t i o n then is an index
-4
of t h e t e m p e r a t u r e . F o r example, to obtain 10 m o l e s / s e c of g a s (2.24 ml at
STP) p e r s e c , f o r P = 20 a t m , M = 40 ( a r g o n ) , T = 2500°K. Putting all quanti-
t i e s in c g s units, we get f o r CIA:

LMEC-Memo-68-10
74
 7 3
1 3 d z n - 13 x 6 x 1019 J40 x 8.3 x 10-x 2.5 x 10
AA=
P N ,/% 20 x 106 x 6 x x 5.2
0

2
= 3 . 6 x l o m 5 c m 2 o r 0.0036 mm

A l a r g e r a r e a will give a l a r g e r volume of g a s , e. g . , if the a r e a of the

pinhole is 0.36 mm', the volume of g a s pumped through will be 224 m l / s e c a t
STP. Under such conditions, the pumping efficiency might b e the limiting
factor. F o r s m a l l hole a r e a , however, the instability of the contour of the
hole a t high t e m p e r a t u r e s is obviously the limiting f a c t o r , especially since a
small change in effective hole area c a n simulate a v e r y l a r g e change i n t e m -
p e r a t u r e ( e . g . , a 10% enlargement of the hole will simulate a 475°K d r o p in
temperature).

M. PNEUMATIC APPARATUS

The volume flow rate of a g a s through a nozzle (above a c e r t a i n c r i t i c a l

value) is proportional t o t h e s q u a r e root of the t e m p e r a t u r e . By comparing
flow r a t e s through two s u c c e s s i v e nozzles, the second being a t a known t e m -
p e r a t u r e , the t e m p e r a t u r e at the f i r s t nozzle can be estimated. This method,
of c o u r s e , is not suitable f o r the m e a s u r e m e n t of t e m p e r a t u r e i n s m a l l v o l u m e s .

This technique has been studied f o r making i n - r e a c t o r high t e m p e r a t u r e

measurements. Its t e m p e r a t u r e i s limited by stable nozzle-flow performance,
however, it should be unaffected by prolonged exposure to t e m p e r a t u r e and to
radioactivity. F o r f u r t h e r details s e e Reference 10, Section 20.

N. PYROMETRIC CONES, TAPES, AND PAINTS

1. P y r o m e t r i c Cones

P y r o m e t r i c cones a r e c e r a m i c compositions with specific melting behavior.

The melting point is not quite fixed, but v a r i e s somewhat with the r a t e of heating.
E a c h cone c a n be used only once and is essentially a kind of fixed point method.

P y r o m e t r i c cones and Holdcroft b a r s a r e made of such m i x t u r e s of m a t e -

r i a l s that d e f o r m a t reaching t e m p e r a t u r e s c h a r a c t e r i s t i c of t h e s e m i x t u r e s .

LMEC -Memo -68 - 10

75
assuming the heating is done at a specified rate. T h e s e devices a r e v e r y popu-
lar i n the c e r a m i c i n d u s t r i e s , w h e r e u s e is made of a whole s e r i e s of cones,
covering the range of about 600 t o 2000°C.

2. Tapes and P a i n t s

The melting points of paints, crayons, pellets, and tapes and t h e change in
color of t e m p e r a t u r e - s e n s i t i v e paints, a r e the b a s i s f o r o t h e r methods of single-
temperature measurements. They a r e often used as low cost, expendable t e m -
pe r a t u r e limit monitor s .

0. PYROELECTRICITY

The phenomenon of pyroelectricity, like its b e t t e r -known s i s t e r piezoelec -

t r i c i t y , m a k e s u s e of the spontaneous polarization of m a t e r i a l s such a s f e r r o -
electrics. Where the l a t t e r depends on mechanical s t r e s s to achieve a change
i n polarization, the f o r m e r utilizes variations in t e m p e r a t u r e to produce the
s a m e result. F o r a given material f a b r i c a t e d into a capacitor of suitable d i -
mensions, the m e a s u r e m e n t of At depends on a m e a s u r e m e n t of c h a r g e A q on
the capacitor. With the aid of a n instrument, like a vibrating-reed e l e c t r o m e t e r ,
t o s e n s e Aq, it i s possible to m e a s u r e t e m p e r a t u r e changes a s small as a mil-
lionth of a d e g r e e . Such a sensitivity would be v e r y useful in c a l o r i m e t r i c mea-
s u r e m e n t s of many kinds, and f o r sensing elements in radiation d e t e c t o r s and
thermometers. F u r t h e r m o r e , since Aq a At, the time derivative of t e m p e r a t u r e
could be d i r e c t l y determined by a m e a s u r e m e n t of c u r r e n t in the pyroelectric
transducer. Materials of high pyroelectric coefficients have been studied over
the t e m p e r a t u r e range of 4.2"K (colemanite) t o m o r e than 1400°C ( b a r i u m z i r -
conium metaniobate).

P. MICROWAVE RESONANT CAVITIES

Two methods using microwaves t o m e a s u r e i n - r e a c t o r t e m p e r a t u r e a r e

appropriately sensitive and could be u s e d to provide long-lived i n - c o r e t e m -
perature measurements.

Experiments with the F r e q u e n c y Shift method demonstrated a sensitivity

of 310 kHz/"C, with a n e a r l y l i n e a r response over the t e m p e r a t u r e range of
3 0 to 1000°C. This method m e a s u r e s t h e change i n resonant frequency of a
A

LME C -Me mo -68 10 -

76
cavity r e s o n a t o r as a function of dimensional changes with t e m p e r a t u r e . With
c u r r e n t methods available f o r m e a s u r i n g R F , a p r e c i s i o n of 0.05"C at 1 0 0 0 ° C
is f e a s i b l e .

In t h e Radiometer method, the n a t u r a l microwave radiation f r o m a b l a c k -

body is m e a s u r e d with a sensitive broadband r e c e i v e r .

A common p r o b l e m with both techniques i s the c o r r o s i o n of s e n s o r s and

input waveguide at elevated t e m p e r a t u r e s . Partial solution of this p r o b l e m
c a n b e provided by evacuating the s e n s o r and waveguide. F u r t h e r work m u s t
be done t o e s t a b l i s h p r o t e c t i v e m e a s u r e s f o r t h e e x t e r i o r of the m e t a l com-
ponents. F o r f u r t h e r d e t a i l s s e e R e f e r e n c e 11.

LIVEC -Me mo -6 8 10 -
77
n
 VI. EFFECTS OF LIQUID METAL REACTOR ENVIRONMENTS ON
TEMPERATURE MEASUREMENT INSTRUMENTS

In addition t o t h e c h e m i c a l and physical effects of association with high

t e m p e r a t u r e liquid metal t h e r e a r e a number of other effects on t e m p e r a t u r e
devices t o be considered. T h e s e a r e : radiation-induced changes i n the c h a r -
a c t e r i s t i c s of the device, radiation-induced spurious signals, vibration, erosion,
and c o r r o s i o n effects.

A. RADIATION DAMAGE

A high energy p a r t i c l e passing through solid m a t t e r may collide o r i n t e r a c t

with a t o m s of the solid m a t e r i a l . This slows the p a r t i c l e , the energy of i n t e r -
action being t r a n s f e r r e d t o the a t o m s . T h e s e a t o m s in t u r n t r a n s m i t energy by
vibration t o t h e i r neighbors. Thus a region of high t e m p e r a t u r e m a t e r i a l is
left i n the t r a c t of the p a r t i c l e , the so-called t h e r m a l spike, which m a y d i s r u p t
the lattice locally. Many a t o m s of the m a t e r i a l may be permanently displaced
f r o m t h e i r n o r m a l positions in the l a t t i c e and come to r e s t a t new positions,
giving r i s e to holes and i n t e r s t i t i a l s . E l e c t r o n s a r e detached f r o m a parent
a t o m and a r e captured by other a t o m s creating ionizations. Neutrons may b e
captured, forming new isotopes which a r e i m p u r i t i e s . Obviously t h e s e phenom-
ena w i l l affect the m a c r o s c o p i c p r o p e r t i e s of the medium. Thus the effects of
radiation ( i n addition t o bulk heating effects) a r e the production of vacancies,
i n t e r s t i t i a l s , impurity a t o m s , and high local t e m p e r a t u r e s .

These effects c a n be roughly grouped into displacement effects and ioni-

zation. In a good conductor, ionization effects rapidly disappear since e l e c t r o n s
may m i g r a t e relatively f r e e l y . In i n s u l a t o r s the ionization effects disappear
much m o r e slowly, the r a t e s being, of c o u r s e , t e m p e r a t u r e dependent. Dis-
placement of a t o m s will r e s u l t in changes i n the mechanical p r o p e r t i e s of a l l
m a t e r i a l s and especiallyaffect the energy level configurations i n s e m i - c o n d u c t o r s .

The m a c r o s c o p i c p r o p e r t i e s m o s t often m e a s u r e d a s a function of radiation

dosage a r e e l e c t r i c a l conductivity, t h e r m a l conductivity, and h a r d n e s s . The
r e a s o n f o r m e a s u r i n g conductivity, which generally d e c r e a s e s with increasing
dosage in m e t a l s , i s to obtain a m e a s u r e of the number of additional e l e c t r o n
scattering c e n t e r s introduced into the medium (shortening of the mean f r e e path).

LMEC-Memo-68 -10
79
T h e t h e r m a l conductivity is affected s i m i l a r l y . The h a r d n e s s of a m a t e r i a l
is usually a m e a s u r e of the n u m b e r of dislocations and the interference among @
dislocations existing in a medium ( s t r a i n hardening).
2
As far as thermocouples a r e concerned, at a dosage of lo1' n / c m metals,
r e f r a c t o r y m e t a l compounds, and i n s u l a t o r s a r e l i t t l e affected. However, t h e
t h e r m o e l e c t r i c power of any couple which depends upon S C, B4C, o r C f o r one
1
of its elements m a y be s e r i o u s l y affected. These m a t e r i a l s have many of the
a t t r i b u t e s of semiconductors, and it is expected that t h e i r electronic p r o p e r t i e s
would b e m o r e s e r i o u s l y changed by radiation damage.

B. RADIATION HEATING

In t h e thermocouple t h e junction and w i r e s might b e heated by the absorbed

radiation at a rate different f r o m that of the surrounding medium. If this is so
then the actual t e m p e r a t u r e of the junction m a y b e higher or lower t h a n t h e bulk
t e m p e r a t u r e of the medium. This type of heating is in addition to the n o r m a l
12
methods of heat t r a n s f e r to the couple. As a n example, in a flux of 10 gamma-
2
r a y s / c m - s e c , a s s u m i n g a n energy loss of 1 m e v p e r event degraded into heat
yields about 0.13 w / c m 3 i n tungsten. Heating due to f a s t neutrons may b r i n g
t h i s f i g u r e up to about 0.2 w / c m
3
.
At high t e m p e r a t u r e s the heat capacity of
tungsten is about 1.0 c a l / c m 3 - " C . Thus t h e r a t e of heating i s about 0.05"C/sec,
which is reasonably s m a l l compared with heating r a t e s t o be encountered in the
r e a c t o r , s o that the n o r m a l m e c h a n i s m of heat t r a n s f e r to a typical t h e r m o -
couple should control its t e m p e r a t u r e .

C. DIFFERENTIAL COMPTON CURRENTS

A spurious signal m a y b e generated in the thermocouple l e a d s if c h a r g e is

lost differentially i n the two w i r e s . If, in the w o r s t c a s e , c h a r g e s w e r e l o s t
in only one lead due t o g a m m a interactions, f o r a w i r e 0.3 mm i n d i a m e t e r and
130 c m of active length, (and a radiation a s in Section B . , preceding) a c u r r e n t
of 1.2 x l o m 8 a m p would flow. F o r a total thermocouple r e s i s t a n c e of 100 ohms
the e r r o r emf will b e i n the o r d e r of 1 p v .

D. IONIZATION CHAMBER E F F E C T S

The passage of ionizing radiation through the g a s s p a c e surrounding the

w i r e s of a thermocouple will produce f r e e e l e c t r o n s and ions. If t h e s e e l e c t r o n s

LMEC-Memo -68 -10

80
and ions a r e f r e e to move they may m i g r a t e to the w i r e s and t h e i r movement
then c o r r e s p o n d s to a c u r r e n t between the w i r e s , tending to shunt the signal
f r o m reaching a n outside indicator.

A typical effect in a gamma f l u x of 10'' g a m r n a - r a y s / c m ' - s e c f o r a total

2 -8
s u r f a c e a r e a for w i r e s of 2.5 c m would be calculated a s 4 x 10 amp ( s e e
R e f e r e n c e 3 , Chapter IV). If the r e s i s t a n c e of a thermocouple c i r c u i t i s 100 ohms
( a high value i s u s e d to allow f o r thin spots which may develop), the voltage
change would then b e 4 g v , o r l e s s than a 1 - d e g r e e e r r o r .

E. THERMIONIC EMISSION

It i s conceivable that a t high t e m p e r a t u r e s t h e r e will be a differential

thermionic e m i s s i o n f r o m the two m a t e r i a l s of which a thermocouple i s c o m -
posed. Little data i s available on the t h e r m i o n i c e m i s s i o n of m e t a l s under
high gas p r e s s u r e conditions. With no accelerating fields p r e s e n t the effect is
v e r y much reduced, However, this effect i s common t o thermocouples o p e r -
ating in other high t e m p e r a t u r e environments and apparently has not caused
noticeable e r r o r s in readings.

F. WATER CYCLE

If w a t e r vapor i s p r e s e n t , a complicated s e r i e s of chemical reactions with

the m e t a l s and insulators c a n b e expected t o o c c u r a t high t e m p e r a t u r e s . The
net r e s u l t i s oxidation of m e t a l s u r f a c e s . The oxide then volatilizes and is
reduced a t a cooler surface, freeing the metal. This s e r i e s of reactions, b e -
sides p e r h a p s inducing electrochemical potentials, would i n c r e a s e the c i r c u i t
lead r e s i s t a n c e , thus enhancing other spurious signals, and p e r h a p s introduce
shunt leakage paths a c r o s s i n s u l a t o r s .

G. ELECTROSTATIC E F F E C T S

The r e a c t o r body will be subjected t o r a t h e r l a r g e frictional and e r o s i v e

f o r c e s , which may tend to c r e a t e l a r g e local e l e c t r o s t a t i c potentials. These
may b e induced into thermocouple w i r e s and p e r h a p s c a u s e ground c u r r e n t s ,
e t c . , which a r e only important h e r e b e c a u s e of the n e c e s s i t y of transmitting a
r a t h e r s m a l l emf over a l a r g e distance t o a n indicator.

LMEC-Memo-68-10
81
H. CHEMICAL E F F E C T S

As an example of a d r i f t effect introduced by c h e m i c a l action, it m u s t b e

r e m e m b e r e d that c a r b o n will r e a c t with tungsten to f o r m a carbide on the s u r -
f a c e of the tungsten w i r e , and that the carbide i s a metallic conductor. If this
o c c u r s a t a thermocouple junction a new thermocouple i s f o r m e d consisting of
the carbide in p a r a l l e l with the main tungsten wire. The emf of the Mo/W2C
junction i s undoubtedly different f r o m that of the Mo/W junction, so that shunting
effects may o c c u r , leading t o drift in the thermocouple output.

Moreover, if the continuity of the tungsten w i r e i s interrupted b e c a u s e c a r -

bide i s f o r m e d a l l the way through the w i r e , the emf of the original thermocouple
m a y not be m e a s u r e d a t all.

I. VIBRATION

Vibration effects will be mainly important because the m a t e r i a l s of which

any sensing unit i s made will b e f a i r l y p l a s t i c a t v e r y high t e m p e r a t u r e s .
Vibration, a s s i s t e d by gravity, may then d e f o r m o r d i s t o r t the device m a t e r i a l s
s o that they might s h o r t out, o r move to undesired configurations.

Local flexure, inasmuch a s i t effects s t r a i n hardening, fatigue, o r local

heat generation, is not expected to be of s e r i o u s concern a t high t e m p e r a t u r e s
b e c a u s e a l l effects a r e soon annealed out.

LME C -Memo -68 10 -

82
 VII. LITERATURE SURVEY

A. THERMOCOUPLE DEVELOPMENT F O R PROJECT ROVER, 2500°C

P r o j e c t Rover seeks to achieve rocket propulsion through t h e u s e of a

n u c l e a r r e a c t o r t o heat hydrogen propellant gas. In o r d e r t o study the t h e r m a l
behavior of the r e a c t o r c o r e (i. e . , heat exchanger) it i s d e s i r a b l e to m e a s u r e
t h e graphite-uranium fuel t e m p e r a t u r e s at many locations simultaneously.
Thermocouples appear to be the only p r a c t i c a l way of doing this. The t h e r m o -
couples, of lengths ranging t o 6 0 in. and d i a m e t e r s limited t o about 1 / 8 i n . ,
have to withstand hydrogen and graphite at as high t e m p e r a t u r e s as possible,
in the p r e s e n c e of a strong nuclear radiation f l u x .

The thermocouples b e s t able t o stand the environment a p p e a r t o b e W v s

W-26Re, insulated by BeO, and encased in a molybdenum o r tantalum sheath.
It is hoped ultimately to be able t o m e a s u r e t e m p e r a t u r e s in the vicinity of
5000"R b 2 5 0 0 " C ) with e r r o r s no w o r s e than a few p e r c e n t .

F i g u r e 28 shows two advanced concepts f o r r e a c t o r c o r e thermocouples.

E a c h of these is to be cooled t o within a few inches of its t h e r m a l junction. In
the bifilar v e r s i o n i n s u l a t o r s a r e shown staggered to i n c r e a s e inter -wire r e -
sistance. The coaxial v e r s i o n has no i n s u l a t o r s at a l l in t h e tip region.

Ultimately it is expected that the maximum dose r a t e s to be experienced

16
by the thermocouples will be ~ 2 . x5 10" n f / c m 2 - s e c ( E >50 kev) o r -2 x 10
7
M e v / c m 2 - s e c andm2 x 10 r a d / s e c of gamma r a y s . The integrated d o s e s will
20
be -10 nfvt and ,lo1 r a d s of g a m m a s . It is believed that t h e s e doses are
not sufficient to affect m a t e r i a l l y the output of the thermocouples. As with all
p a r t s of the r e a c t o r , t h e thermocouples would melt if not p r o p e r l y cooled.

Rough calculations and a test in the Omega W e s t R e a c t o r have shown that

radiation contributions to the shunt effect, either through gaseous conduction
o r ionization in t h e BeO, should not b e significant in comparison to t h e t h e r m a l
shunt effect d i s c u s s e d in the preceeding text.

B. HIGH-TEMPERATURE THERMOMETRY

R e f e r e n c e s 8 and 10 a r e the publications of seminars on work done i n high

temperature thermometry. They contain much detailed information b a s e d on
fundamentals covered in the preceding sections of t h i s document.

LME C - Me mo -68 - 10
83
 \ TUNGSTEN-RHENIUM
CONDUCTOR
- - .- - - - .
VAPOR DEPOSITED
[TUNGSTEN COAT
,007" THICK
r TANTALUM OR VAPOR DEPOSIT€:D
TUNGSTEN TIP
TANTALUM OR MOLYBDENUM SHE ATH
f

\
T 2 I 1 \TUNGSTEN CONDUCTOR
Be 0 INSULATORS, SINGLE
HOLE TUBING, STAGGERED
IN TIP PORTION

a.BlFlLAR TC T I P

VAPOR DEPOSITED TUNGSTEN

.OlO 1 DIA. COAT .007" THICK
W - 26% Re WIRE
7 \ .008"W A L L
r V A P O R DEPOSITED TIP
TANTALUM OR MOLYBDE.NUM SHEATH

L E DDRILL
M HOLES
FOR TC LEADS
2" + i.OIO
-Be

DIA TUNGSTEN WIRE

0 INSULATORS

b.COAXlAL TC TIP
5-2-68 UNCL
7694-55233
F i g u r e 28. Advanced Thermocouple Concepts
C. FAST RESPONSE THERMOCOUPLE

Reference 12 d e s c r i b e s thermocouples made of 0.001-in. and 0.0005-in. wire.

The 0.0005-in. thermocouple reached a nominal 100% of t e m p e r a t u r e in l e s s than
1 m s e c a f t e r a s t e p function change. This r e p r e s e n t s a t i m e constant of about
200 p s e c .

D. FUEL-PIN TEMPERATURE MEASUREMENT

Reference 13 d i s c u s s e s the development of instrumenation and t e s t equip-

ment f o r U 0 2 fuel-pin t e m p e r a t u r e m e a s u r e m e n t s t o 2760°C (5000°F). T h e r m o -
couples w e r e selected as providing the b e s t technique, s e v e r a l t y p e s w e r e t e s t e d
and the cables and t h e i r insulation a r e d i s c u s s e d .

E. THERMOCOUPLE STABILITY AND RELIABILITY IN LIQUID METAL

References 14 and 15 r e l a t e specific experiences with the u s e of sheathed

thermocouples i n liquid m e t a l s y s t e m s . Essentially, the sheath m a t e r i a l and
fabrication must protect t h e thermocouple f r o m the liquid m e t a l environment
while not introducing a t h e r m a l lag between thermocouple and point to be m e a -
sured. A life as low a s 25 h r a t 1850°F was experienced. Repeatabilities a s
good as 5 ° F a t 1000°F a f t e r 2100 h r i n sodium w e r e obtained.

F. THERMOCOUPLE DEVELOPMENT FOR A LITHIUM-COOLED REACTOR

Reference 16 i s a comprehensive, in-depth and well illustrated r e p o r t on

t h e r e s e a r c h , development and t e s t of thermocouples f o r u s e i n a liquid m e t a l
reactor. The p r i m a r y subject of study i s the W-5RelW-26Re thermocouple,
but a l s o , included a r e the following: Chrome1 /Alumel, W -3Re/W -25Re, Mo / C b ,
and M o / W -26Re.

G. THE E F F E C T OF PRESSURE ON TEMPERATURE CALIBRATION

In R e f e r e n c e 17, the effect of p r e s s u r e on the emf of Mo/Mo - 50% R e

thermocouples a s c o m p a r e d to Cr/A1 w a s small, about 7 ° C at 4 0 kbar and
1000°C. It is believed that s t r a i n on thermocouple w i r e s caused by deformation
in h i g h - p r e s s u r e s y s t e m s has a significant effect on the m e a s u r e d t e m p e r a t u r e s .
F o r example, it h a s been reported that C r / A l thermocouples will r e a d as much
as 8 ° C low at 700°C a f t e r cold work.

LMEC -Memo -68 - 10

85
 The advantage of Mo and Mo-Re alloys f o r u s e a s thermocouples in high-
p r e s s u r e dies is t h e i r ability t o resist pinching off when t h e s e w i r e s a r e led
through gasketed s y s t e m s . They have been proven t o r e s i s t breaking much
b e t t e r than C r / A l o r P t / P t - R h . Welding of Mo/Mo-Re thermocouples is dif-
ficult since the r e c r y s t a l l i z a t i o n t e m p e r a t u r e of the Mo is reached and a v e r y
b r i t t l e junction is f o r m e d . The problem w a s solved by brazing the joint with
platinum. This procedure, however, limits the useful t e m p e r a t u r e t o slightly
over 1700°C, but the advantage of a ductile couple junction in most c a s e s out-
weighs the disadvantages. The effect on emf of the platinum in the junction w a s
small enough s o that it w a s not detected when p r e c i s e calibration of t h e couples
was made.

Output of the Mo/Mo - 5070-Re thermocouple w a s found t o b e about twice

that of Pt/Pt - lO%-Rh.
Investigation of a thermocouple s y s t e m that would have t h e above advan-
tages and a l s o stand d i r e c t welding led t o R e / M o - 3070-Re. This couple will
r e t a i n ductility during d i r e c t r e s i s t a n c e welding but h a s a smaller emf output,
being about equal to Pt /Pt - 1070-Rh.

H. GRADIENT APPROACH TO THERMOCOUPLE CIRCUITRY

Reference 18 is a brief, but v i t a l , discussion of the underlying principles

of thermocouple t h e r m o m e t r y . If not p r o p e r l y understood, the unwary u s e r
m a y introduce e r r o r s i n the o r d e r of t e n s of d e g r e e s when making a t r a n s i t i o n
f r o m thermocouple w i r e t o extension leadwire, even though h e u s e s a n i s o -
t h e r m a l junction block.

Another typical problem which c a n lead t o l a r g e calibration e r r o r s involves

thermocouples that have b e e n in u s e a long time and a r e removed f o r a c a l i -
b r a t i o n check. As a r e s u l t of alloy recomposition along the length of the t h e r m o -
couple w i r e , t h e r m a l gradient emfs along one w i r e m a y r e s u l t i n operation
which does not a p p e a r when just the couple end is i n s e r t e d into a t e s t block.
The welded couple m a y check out t o be i n perfect calibration on the t e s t r i g but
when placed i n operation m a y b e aided or opposed by the o t h e r emfs.

LME C - Memo -68 - 10

86
 REFERENCES
n

M a t e r i a l w a s drawn f r e e l y f r o m the following s o u r c e s :

1. "Temperature, Its Measurement and Control i n Science and Industry,

Vol. I, 11, and III,tt(Reinhold Publishing G o r p . , New York, 1941)

2 . R. P. Benedict, " T e m p e r a t u r e and Its M e a s u r e m e n t , ' ' Electro-Technology,

July 1963

3 . B. Ragent and A. H. Samuel, "An Investigation of T e m p e r a t u r e Measuring

Techniques f o r Use i n High P o w e r Density Nuclear R e a c t o r s , " Broadview
R e s e a r c h and Development, Document No. UCRL-5303, Published 1957

4. W. F. R o e s e r and S. T . Lonberger, !'Methods of T e s t i n g Thermocouples

and Thermocouple Materials," NBS C i r c u l a r 590, F e b r u a r y 1958
(Government Printing Office, Washington, D. C. )

5. "Status of Instrument Development f o r the SNAP-50 Reactor T e s t P r o g r a m s , "

September 1965, PWAC-473, P r a t t and Whitney A i r c r a f t Company

6 . F. R. Caldwell, I'Thermocouple M a t e r i a l s , ' ' NBS Monograph 40, March 1962,

(Government Printing Office, Washington, D. C.

7. "Standards and P r a c t i c e s f o r Instrumentation," published by Instrument

Society of A m e r i c a , Section C96.1, 1964, A m e r i c a n Standard f o r T e m p e r a -
t u r e M e a s u r e m e n t T e rmocouples

8. "High T e m p e r a t u r e T h e r m o m e t r y S e m i n a r , ORNL October 1959," published

by AEC, Division of Technical Information, TID-7586

9 . "Ultrasonic Instrumentation f o r the Measurement of T e m p e r a t u r e , I ' f r o m

Applications of Ultrasonic Energy, Ultrasonic Instrumentation f o r Nuclear
Applications, Bi-Monthly P r o g r e s s r e p o r t , D e c e m b e r 1966, NY03622-6

10. ,
"High T e m p e r a t u r e T h e r m o m e t r y , S e m i n a r , Washington, D. C . F e b r u a r y
1965," published by AEC, Division of Technical Information, Wash-1067

11. T. R. Billeter and D. P. Brown, "Microwave M e a s u r e m e n t of High T e m -

p e r a t u r e s Within Nuclear R e a c t o r s , I n t e r i m Report," BNWL-399, October
1967, Battelle Northwest L a b o r a t o r y

12. G. R. Dittbenner, "Development and Application of t h e Intrinsic T h e r m o -

couple f o r Fast Response,'' Lawrence Radiation L a b . , UCRL-14593,
March 1966

13. G. F. Popper and A. E. Knox, "Faret In-Core Instrument Development,"

ANL-7 16 1, July 1966

14. J. W. S t a r k , "Final Report on the T e s t s and Development P r o g r a m of MgO

Sheath -Type Thermocouples , I 1 M a r y 1955, AEC Document, KAPL -ADM - 12 7 0

LME C - Memo -68 - 10

87
15. "Space P o w e r and Propulsion Section, F i r s t Quarterly Report, September
1962," AEC Document, NP-12433
@
16. "Thermocouple Development f o r a Lithium-Cooled Reactor Experiment,''
PWAC-422, M a r c h 1964, Pratt and Whitney A i r c r a f t

17. H. D. Stromberg and D. R. Stephens, "Effect of P r e s s u r e on the T e m p e r a -

t u r e Calibration of Mo/Mo - 5070-Re Thermocouples t o 1000°C and 60 Kilo-
,"
b a r s UCRL- 1499 3

18. R. J. Moffat, "The Gradient Approach to Thermocouple Circuitry,"

,
Gener a1 Mot o r s R e s e a r c h L a b o r a t o r i e s W a r r e n , Michigan

19. "Temperature, Its M e a s u r e m e n t and Control i n Science and Industry,

Part 2," (Reinhold Publishing Corporation, New York 1962)

20. H. D. Baker, E. A. R y d e r , and N. H. B a k e r , "Temperature Measurement

i n Engineering,'' (John Wiley and Sons, New York, 1953) Vol. 1, Vol. 11,
196 1

21. K. S. Lion, "Instrumentation in Scientific R e s e a r c h , " (McGraw-Hill Book

Company, New York, 1959)

22. T. R . H a r r i s o n , "Radiation P y r o m e t r y and Its Underlying P r i n c i p l e s of

Radiant Heat T r a n s f e r , ' ' (John Wiley and Sons, New York, 1960)

23. L. G. Rubin, "Temperature-Concepts, Scales and M e a s u r e m e n t Techniques,"

Technical Memorandum T-538 i s s u e d by R e s e a r c h Division of Raytheon
Company

24. "Accuracy i n M e a s u r e m e n t s and Calibrations, 1965," U. S. National Bureau

of Standards Technical Note 262 (Government Printing Office, Washington,
D. C. )

25. W. E. F o r s y t h e , "Measurements of Radiant Energy," (McGraw -Hill,

New York 1937)

26. P. H. Dike, " T e m p e r a t u r e M e a s u r e m e n t s with Rayotubes," Leeds and

Northrup Company, Philadelphia, 1953

2 7 . p. H. Dike, "Thermoelectric T h e r m o m e t r y , ' ' Leeds and Northrup Company,

Philadelphia, 1958, 3 r d Edition

28. Electro-Technology, May 1963, pp 113 -128

29. Electro-Technology, July 1963, pp 71-86

30. International Science and Technology, Prototype I s s u e , pp 18-27

31. International Science and Technology, June 1962, pp 36-53

LME C -Memo -6 8 - 10
88
/, 3 2 . Instruments and Control S y s t e m s , May 1961, pp 841-853
U 3 3 . H. J. Metz and M. M. Yarosh. "Experiences and Development in Instru-
mentation for Liquid Metal Experimknts , I 1 F o u r t h High T e m p e r a t u r e Liquid
Metal Heat T r a n s f e r Technology Conference, September 1965

LME C - Memo -68 10 -

89
 APPENDIX

A. FUNDAMENTALS OF TEMPERATURE MEASUREMENT

1. Definition of T e m p e r a t u r e

T e m p e r a t u r e is defined a s the condition of a body which d e t e r m i n e s the

t r a n s f e r of heat to o r f r o m o t h e r bodies. P a r t i c u l a r l y it i s a manifestation of
the a v e r a g e t r a n s l a t i o n a l kinetic energy of the molecules of a substance due
to heat agitation.

T e m p e r a t u r e is a n intensive quantity. This m e a n s that t h e combination of

two identical objects having the s a m e t e m p e r a t u r e will yield a new body with
twice the mass and volume (extensive quantities) of each component but with the
same temperature. A s a consequence, any t e m p e r a t u r e m e a s u r i n g s y s t e m
m u s t e s t a b l i s h both a r e f e r e n c e t e m p e r a t u r e and a r u l e f o r m e a s u r i n g the dif-
f e r e n c e s between the r e f e r e n c e and any other t e m p e r a t u r e s . In principle n e a r l y
e v e r y p r o p e r t y of a m a t e r i a l which changes with t e m p e r a t u r e in a well-defined
way can s e r v e as a t h e r m o m e t r i c substance. The v a r i e t y of such s y s t e m s i s
tremendous. Although a r b i t r a r y s c a l e s m a y validly conform t o definite t e s t
p r o c e d u r e s , it is obvious that a t r u l y u n i v e r s a l s c a l e , one which is e a s i l y and
fundamentally defined, is far m o r e d e s i r a b l e .

L o r d Kelvin proposed a thermodynamic s c a l e which was independent of the

m a t e r i a l used o r of the specific details of the experiment. It may be explained
v e r y briefly a s follows: a s s u m e a perfect r e v e r s i b l e heat engine t r a n s f e r r i n g
heat f r o m one infinite capacity heat r e s e r v o i r t o another. If Q1 i s the quantity
of heat taken f r o m one r e s e r v o i r and Q is t h e quantity put into the o t h e r , then
2
the t e m p e r a t u r e s of the two r e s e r v o i r s T and T a r e given by
1 2

- *1
---q
T2 *

O r , in o t h e r words, the t e m p e r a t u r e s of two heat r e s e r v o i r s a r e related to

each other in proportion t o the heat quantity contained in each. A temperature
s c a l e m a y then b e completely defined by establishing one fixed point relative to

LMEC -Memo -68 - 10

91
absolute z e r o . Kelvin chose t h i s point s o that his thermodynamic s c a l e would
be simply r e l a t e d to the then existing centigrade scale.

2. International P r a c t i c a l T e m p e r a t u r e Scale (IPTS)

In 1954 t h e s c a l e w a s adjusted slightly by choosing the t e m p e r a t u r e of t h e

t r i p l e point of w a t e r to b e 273.16"K exactly. T h i s t e m p e r a t u r e , t h e s t a t e at
which solid, liquid and vapor phases of w a t e r a r e i n equilibrium, c a n be mea-
s u r e d with a p r e c i s i o n of a few ten-thousandths of a d e g r e e . In view of t h e f a c t
that the Kelvin thermodynamic scale is identical with that defined by t h e gas
e qua tion

PV=RT ,

it is possible t o reduce Kelvin's s c a l e t o p r a c t i c e . At the p r e s e n t time, t h e gas

t h e r m o m e t e r , filled with a p e r f e c t g a s , is recognized a s t h e p r i m a r y i n s t r u -
ment f o r realizing the thermodynamic s c a l e over the range that the t h e r m o m e t e r
c a n be used. Although a g r e a t deal of e f f o r t h a s gone into t h i s type of work, g a s
t h e r m o m e t r y r e m a i n s a difficult and tedious p r o c e d u r e , g e n e r a l l y unsuited to
t h e p r a c t i c a l needs of t e m p e r a t u r e m e a s u r e m e n t . F o r t h i s r e a s o n the IPTS was
originated in 1927, with i m p o r t a n t r e v i s i o n s in 1948 and minor changes s i n c e
that time. It w a s e s t a b l i s h e d t o r e p r e s e n t , in a p r a c t i c a l m a n n e r , the t h e r m o -
dynamic s c a l e a s closely as possible.

The IPTS is defined by a s e t of fixed points and r u l e s governing interpolation

between t h e m and extrapolation beyond. At one of t h e s e fixed points, the t r i p l e
point of w a t e r , t h e two s c a l e s a r e in exact a g r e e m e n t . F i v e o t h e r reproducible
equilibrium t e m p e r a t u r e s a r e denoted as fixed points: the boiling points of
liquid oxygen, w a t e r , and sulfur, and t h e f r e e z i n g points of s i l v e r and gold.
T h e s e t e m p e r a t u r e s , covering a range f r o m - 182.97 t o t 1063 .O" C, w e r e assigned
on the b a s i s of g a s t h e r m o m e t e r m e a s u r e m e n t s p e r f o r m e d as c a r e f u l l y a s t h e
state -of - t h e - a r t p e r m i t t e d . Interpolation between t h e fixed points is a r r i v e d a t
by different methods f o r different r a n g e s .

Thus, between the oxygen point and 630.5"C, the r e s i s t a n c e of a platinum

r e s i s t a n c e t h e r m o m e t e r i s used in conjunction with two equations, one below
t h e t r i p l e point and one above. The emf of a P t - P t / l O R h thermocouple and

LME C -Memo - 68 - 10
92
its a s s o c i a t e d equation defines the interpolation range between 630.5"C and the
gold point. Extrapolation of the s c a l e above the gold point i s accomplished
through the u s e of the Plant radiation f o r m u l a , implemented by optical radiation
p y r o m e t r y . No upper l i m i t is a s s i g n e d to the scope of the IPTS, but a lower
limit is the oxygen point, 90.19"K. By calibrating a s e r i e s of platinum r e s i s -
tance t h e r m o m e t e r s against a helium g a s t h e r m o m e t e r , the National Bureau of
Standards has established a provisional s c a l e between 11 and 9 0 ° K .

Although the IPTS is actually nothing m o r e than a p r a c t i c a l s t a n d a r d e m p i r i -

c a l t e m p e r a t u r e s c a l e , i t s advantages have made possible the m o s t significant
fact of all. Any competent l a b o r a t o r y may now s e t up equipment f o r a t h e r m o m -
e t e r c a l i b r a t i o n in t e r m s of fixed-point s t a n d a r d s , without r e f e r e n c e t o any other
l a b o r a t o r y , with confidence t h a t the r e s u l t s will be c o n s i s t e n t and in a g r e e m e n t
with all other competent l a b o r a t o r i e s . T h i s is the m o s t b a s i c r e q u i r e m e n t f o r
any m e a s u r ement s y s t e m .

Table A-1 p r o v i d e s a r e f e r e n c e of s o m e of t h e m o r e significant t e m p e r a -

t u r e points.

B. DEFINITIONS

The following definitions a r e l i s t e d h e r e t o provide a convenient r e f e r e n c e

f o r t e r m s commonly a s s o c i a t e d with t e m p e r a t u r e m e a s u r e m e n t s .

Adiabatic - A change undergone by a body when its condition is

a l t e r e d without gain o r loss of heat.

Blackbody - a body in which all the energy is a b s o r b e d f o r a l l values

of the wavelength of the incident radiant energy.

Btu
__ - B r i t i s h t h e r m a l unit, t h e quantity of heat r e q u i r e d to r a i s e the
t e m p e r a t u r e of 1 lb of w a t e r 1°F a t , o r n e a r , its point of m a x i m u m
density (39.1 OF);it is equivalent to 252 international c a l o r i e s .

Calorie - The amount of h e a t n e c e s s a r y to r a i s e 1 g m of w a t e r 1 "C

for w a t e r at 15°C ( c g s s y s t e m ) . The international c a l o r i e is defined
as 1 / 8 6 0 w - h r .

Heat Capacity
-
- The quantity of heat r e q u i r e d to i n c r e a s e the t e m -
p e r a t u r e of a s y s t e m o r substance by one d e g r e e .

LME C - Me mo - 6 8 - 10
93
 TABLE A-1
TEMPERATURE CALIBRATION POINTS

- - ~ .

Degrees Degrees Degrees Degrees

Significant P o i n t s Kelvin Celsius Fahrenheit Rankine
( O K ) ("C) (OF) (OR)
Absolute Z e r o 0 -273.15 -459.67 0
Helium Boils 4.2 -269 -452 7.6
Hydrogen Boils 20 -253 -423 36
Neon Boils 27 - 246 -410 49
Nitrogen Boils 77 - 196 -3 20 139
Argon Boils 87 - 186 -3 02 157
Oxygen Boils 90 -183 -297 162
Carbon Dioxide Sublim 195 -7 8 -109 350
M e r c u r y Melts 234 -39 -38 42 1
Ice Melts 273.15 0 32 49 1.67
T r i p l e Point of W a t e r 273.16 0.0100 32.0180 49 1.69
W a t e r Boils 3 73 100 212 67 1
T i n Melts 5 05 232 4 49 908
M e r c u r y Boils 630 357 674 1133
Zinc M e l t s 6 93 420 7 87 1246
Sulfur Boils 7 18 445 832 1291
Antimony Melts 9 03 63 0 1166 1625
Silver Melts 1234 96 1 1762 222 1
Gold M e l t s 1336 1063 1945 2404
Iron Melts 1809 1536 27 96 3255
P l a t i n u m Melts 2047 1774 3224 3683
Aluminum Oxide M e l t s 2293 2020 3632 409 1
Molybdenum Melts 2893 2620 47 48 5207
Tantalum Melts 3300 3 027 5480 5939
Tungsten Melts 3643 337 0 61 10 6569
C a r b o n Sublimes 4473 4200 76 00 8059
Molybdenum Boils 5073 4800 8670 9129
Tungsten Boils 6 173 5900 10,650 11,109

LME C -Memo -68 10 -

94
 . ............ .._

6 Heat Quantity - The amount of heat t h a t m u s t be added to ( o r removed

f r o m ) a s y s t e m , o r substance, ( e x p r e s s e d i n c a l o r i e s o r Btu) to r a i s e
(or lower) its t e m p e r a t u r e by one d e g r e e .

Latent Heat of Fusion

~
- The quantity of heat n e c e s s a r y to change
1 g m ( c g s s y s t e m ) of solid to a liquid with no t e m p e r a t u r e change.

Latent Heat of Vaporization - The quantity of heat n e c e s s a r y to change

one g r a m ( c g s s y s t e m ) of liquid to vapor without change of t e m p e r a t u r e .

Pyrometry - In a broad s e n s e the t e r m s p y r o m e t r y and t h e r m o m e t r y

a r e equivalent. P y r o m e t r y has b e c o m e commonly a s s o c i a t e d with
high t e m p e r a t u r e m e a s u r e m e n t , and even m o r e specifically with
measurement a t a distance. T h e r m o m e t r y i s the m o r e g e n e r i c t e r m .

Seebeck Effect - The effect manifest in a c i r c u i t consisting of two

different m e t a l s with one junction hotter than the o t h e r resulting in
a c u r r e n t flow through the c i r c u i t (thermocouple).

Specific Heat - The r a t i o of the t h e r m a l capacity of any substance to

t h a t of water at 15 " C .

12 Stefan-Boltzman Law of Radiation - The e n e r g y radiated in unit t i m e

by a blackbody is given by, E t K ( T 4
t e m p e r a t u r e of the body, T
0
roundings, and K is a constant.
- T 4), w h e r e T is the absolute
0
i s the absolute t e m p e r a t u r e of the s u r -

13 T h e r m a l Capacity of a Substance - The quantity of heat n e c e s s a r y to

produce a unit change of t e m p e r a t u r e in a unit m a s s ; numerically
equivalent to specific heat.

_-Thermodynamics, Laws of -
I. When mechanical work i s t r a n s f o r m e d into h e a t , o r heat into
mechanical work, the amount of work is always equivalent t o
the quantity of heat.

11. It i s impossible by any self-sustaining p r o c e s s f o r heat t o b e

t r a n s f e r r e d f r o m a colder to a hotter body.

LMEC-Memo-68-10
95
 15) Thomson T h e r m-
o e l e c t r i c Effect - The designation of the potential
gradient along a conductor which accompanies a t e m p e r a t u r e gradient.
The magnitude and direction of the potential v a r i e s with the substance.

16) Vapor P r e s s u r e - The pressure exerted when a solid o r liquid i s in

equilibrium with its own vapor. The vapor p r e s s u r e i s a function of
the substance and the t e m p e r a t u r e .

17) Wien's Displacement Law -When the t e m p e r a t u r e of a radiating

blackbody i n c r e a s e s , the wavelength corresponding to m a x i m u m
energy d e c r e a s e s i n such a way t h a t t h e product of the absolute tem-
p e r a t u r e and wavelength is constant.

1max T = w

w is known a s Wiens displacement constant.

C. COLOR SCALE O F TEMPERATURE

Table A-2 is a n effort to i n t e r p r e t , i n terms of t h e r m o m e t r i c readings,

commonly used e x p r e s s i o n s describing t e m p e r a t u r e s .

TABLE A-2
COLOR SCALE O F TEMPERATURE

__.______

i Color T e m p e r at u r e
~~~~~
("C) I (OF)

Incipient Red Heat 500 t o 550 900 t o 1000

Dark Red Heat 650 750 1200 1400
Bright Red Heat 850 95 0 1500 1750
Yellowish Red Heat 1050 1150 1900 2 100
Incipient White Heat 1250 1350 2300 2450
White Heat 1450 1550 265 0 2850

LMEC-Memo-68-10
96