NATIONAL BUREAU OF STANDARDS REPORT

7836

CURRENT NBS EFFORTS TOWARD DEVELOPMENT

OF THERMAL CONDUCTIVITY REFERENCE STANDARDS

Complementary Report

March 1963

by

D. R. Flynn

to the

Bureau of Ships

Department of the Navy

Washington, D. C,

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

NATIONAL BUREAU OF STANDARDS REPORT

MBS PROJECT NBS REPORT

1006-20-10461 March 25, 1963 7836

CURRENT NBS EFFORTS TOWARD DEVELOPMENT

OF THERMAL CONDUCTIVITY REFERENCE STANDARDS

by

D. R. Flynn

Heat Transfer Section

Building Research Division

Complementary Report to the

Eureau of Ships

Department of the Navy

Washington, D. C.

INDEX NO. S-R007 12 01, Task No. 800

(BuShips 1700S-716-62) • Code 2781

IMPORTANT NOTICE NATIONAL BUREAU OF ST

for use within the Government, and review. For this reason, the whole or in part, is not author Bureau of Standards, Washingtoi

the Report has been specifically

Approved for public release by the

Director of the National Institute of

Standards and Technology (NIST)

on October 9, 2015.

s accounting documents intended

subjected to additional evaluation

listing of this Report, either in Office of the Director, National

1 the Government agency for which

ipias tor its own use. <NBp>

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

CURRENT NBS EFFORTS TOWARD DEVELOPMENT

OF THERMAL CONDUCTIVITY REFERENCE STANDARDS

TABLE OF CONTENTS

, PAGE

ABSTRACT 1

1. INTRODUCTION 1

2. ARMCO IRON. • • . 2

3. LEAD. 6

4. INCONEL 702 8

,

• i

• 5,. PYROCERAM CODE 9606 .....

. .

13

6. PYREX GLASS' . 15

7. REFERENCES 18

LIST OF TABLES

Table 1. Thermal Conductivity of a Batteile Armco Iron 3

Table 2. Deduced Thermal Conductivity of Lead 6

Table 3* Thermal Conductivity of Inconel 702 9

Table 4. Correlation between Thermal Conductivity and Electrical

Resistivity of Solution Annealed Inconel 702............. 12

\
• *

•

... , . v

,..

.
TABLE OF CONTENTS (Cont'd)

PAGE

List of Tables (Cont'd) :

Table 5. Thermal Conductivity and Resistivity of Pyroceram

Code 9606 13

Table 6. Deduced Values for the Thermal Conductivity of

Pyrex Glass • 16

LIST OF FIGURES

Figure 1. Thermal (Conductivity of Armco Iron (sample supplied

by Battelle Memorial Institute), The upper drawing

shows the departures of the NPL results from those

obtained at NBS . . . . ... 5

Figure 2. Deduced values for the Thermal Conductivity of Lead.

The upper drawing shows departures of data of various

investigators from the deduced values 7 Figure 3- Thermal Conductivity of Inconel 702 in the solutionannealed condition (MJ P > A) and in the age-hardened

condition (A‘,S). The upper drawing shows departures

of the smoothed results obtained in several apparatus... 11

Figure 4. Thermal Conductivity and Thermal Resistivity of

Pyroceram Code 9606 Microcrystalline Glass 14

Figure 5. Deduced values for the Thermal Conductivity of

Pyrex Glass. The upper drawing shows departures of

data of various investigators from the deduced values... 17

CURRENT NBS EFFORTS TOWARD DEVELOPMENT

OF THERMAL CONDUCTIVITY REFERENCE STANDARDS

Complementary Report

March 1963

by D. R. Flynr

ABSTRACT

This report discusses the efforts which are currently being made at

the National Bureau of Standards in the direction of developing suitable

thermal conductivity reference standards:

1. Armco Iron - NBS data are presented for the thermal conductivity

of Armco iron over the temperature range from -160* to 640*0. Below 400°C

the NBS results are; within 1 percent of those obtained by R, 11 . Powell of

the National Physical Laboratory on a specimen from the same lot.

2. Lead - A comparison is given of published values of the thermal

conductivity of lead over the temperature range from -250* to 3Q0*C. This

review was made as a preliminary to possible determination of the thermal

conductivity of NBS freezing point lead.

3. Inconel 702 - Thermal conductivity results obtained by four independent methods at NBS are given over the temperature range from -150° to

1200°C. For samples of this alloy having similar thermal histories, the

smoothed results are within about 1 percent of a smooth curve.

4. Pyroceraxn Code 9606 - Measurements have been made over the temperature range 200* to 1000*0 by one method j the thermal conductivity

values obtained were 0.035 w/cm C at 2GQ d C and 0,023 w/cm C at 1QQ0*C.

Additional measurements by other methods are in progress.

5. Pyrex Glass (Code 7740) - A brief survey of published data on

the thermal conductivity of Pyrex over the temperature range 0* to 500 *C

is given* Some unpublished NBS data are included. Additional NBS measurements are planned.

This report is a slightly modified version of a paper given by the

author at the Second Conference on Thermal Conductivity held at the National

Research Council of Canada, Ottawa, Canada, on October 10-12, 1962. It is

1. INTRODUCTION

- 2-

being made available as an NBS report in the belief that the contents may

be of general interest. This report discusses the efforts which are currently being made at NBS with the aim of developing suitable thermal conductivity reference standards. Many of the considerations involved in the

selection and use of reference standards are discussed in a separate report

[i]-7.

In the discussion below, thermal conductivity data are presented which

have not been formally published. All such data are subject to review,

editorially and otherwise, prior to formal publication, and their preliminary status should be recognized.

2. ARMCO IRON

Powell [2] has recently reviewed the numerous published data now

available on the thermal conductivity of Armco iron and derived "most

probable values," which are estimated to be good within ±2 percent from

0° to 600^0, and within about ±5 percent at 1000°C. The range of experimental values in the literature, however, is about 7 percent between 0°

and 600 &C, and increases to almost J>0 percent at. 1000°C. In an attempt to

resolve this discordance of experimental results, C. F. Lucks of the Battelle

Memorial Institute proposed a round-robin of thermal conductivity measurements on Armco iron. The Battelle Memorial Institute obtained samples of

Armco iron in the form of 1-Inch diameter rods, annealed them for half an

hour at 850 a C, and distributed samples to: National Physical Laboratory,

Teddingtan, England; National Research Council, Ottawa, Canada; and National

Bureau of Standards, Washington, D. C. , U.S.A. , and later to a number of

other laboratories. R. W. Powell, et al. have reported [ 3 ] the NPL measurements over the temperature range from -200° to lOOO^C; M. J. Laubitz

has reported [4] the NRC measurements from 3 G

0 to 1000°C.

The sample of Armco iron supplied to NBS by Battelle was in the form

of a round bar, nominally 1 inch in diameter and 3 9 inches in length. The

ends of this sample were stamped No. 3 and No. 4, the No. 3 and being immediately adjacent to the sample sent to the National Physical Laboratory,

and the No. 4 end adjacent to the sample sent to the National Research

Council. This Armco iron was stated to have been obtained from the American

Rolling Mill Company, Hamilton, Ohio. The ladle analysis in weight percent

,

as given by the supplier, is as follows; C 0.02, Mn O.OpO, P 0.006, S 0.023,

Si 0.004, Cu G.O83 , Fe (by difference) 99.834. Powell [ 3 ] reported that an

NPL analysis showed no significant variation from the analysis given above,

other than the presence of O.O83 percent Ni.

1/ Figures In brackets indicate the literature references at the end of

this report.

TABLE 1

THERMAL CONDUCTIVITY* OF BATTELLE ARMCO IRON

Temperature KBS • NPL "Most Probable"

On k k k

-160 0.887 0.893** 0.7 —

-150 .873 .879 0.7

-100

| .815 .820 0.6 — l -50 .775 .778 0.4 —

0

' .742 .747 0.7 0.749 • 0.9

50 .712 .719 1.0 —

100 .632 . 686 • 0.6 .672 -1.5

ISO .652 . 654 0.5 ----

200 .620 .621 0.2 . 608 -1.9

250 .587 .588 O'. 2 —

fA oo .554 .555 0.2 .548 -1.1

550 .523 .525 0.4 —

400 .495 .452 -0.6 .487 -1.6

450 .469 .460 -1.9 ----

500 .445 .430 -2.9 .433 -2.3

550 .417 .405 -2.9

600 .391 .332 -2.3 .389 -0.5

640 .371 . 564** -1.9

* Watt/ cm deg C ** Interpolated

-4-

The NBS Heat Transfer Section has completed measurements of the thermal

conductivity of the Bat telle Armco sample over the temperature range from

-160° to 640 °C. These measurements were made in the NBS metals apparatus,

which has been described by Watson and Robinson [5], In brief, the measurement was made by determining the electrical power input to a heater in one

end of a specimen 3?*

0

err; long and 2.3^6 cm in diameter, which was cooled

at the other end by circulating water or liquid nitrogen. Temperatures

were measured by means of thermocouples at seven locations, 3*51 cm apart,

along the central portion of the bar, thus permitting the calculation of

six thermal conductivity values, each at a different, mean temperature, for

each thermal equilibrium. A guard cylinder, concentric with the specimen,

was used to minimize heat exchanges between the specimen and the surrounding insulation, and corrections were made for such heat exchanges.

Twelve data points were obtained in the temperature range from -160°

to 192 <'C in the NBS low- temperature metals apparatus [5], using 0.40 mm

diameter chromel jalumel thermocouples, diatomaceous earth insulation in

air, and liquid nitrogen coolant. Eighteen data points were obtained in

the temperature range from 90° to 508 aC in the NBS high- temperature metals

apparatus [6], using O .38 mm diameter platinum- 10% rhodium: platinum thermocouples, fine powdered alumina insulation flushed with 4 liters/hr of dry

nitrogen gas, and 40°C water coolant. Eighteen additional data points

were obtained in the temperature range from 125° to 650°C in the high temperature apparatus, using a new heater, the same thermocouples, the same

alumina insulation evacuated to about 15 Torr, and 40 c'C water coolant.

Table 1 presents the smoothed NBS results at 50 deg C intervals.

Powell's data on the Batcelle Armco are given in the third column with

percent departures (NBS - 100) in the fourth column. Powell's "most

probable values" are given in the fifth column, with percent departures

(NBS ~ 100) in the sixth column.

The solid line in the lower drawing of Figure 1 represents the NBS

data given in Table 1; the broken line represents Powell's results for

Battelle Armco (Table 1, column 3)* The upper drawing in Figure 1 shows

the percent departures of the NPL data from those obtained at NBS (Table

1, column 4).

The NBS results have not yet been corrected for the effects of longitudinal heat flow in the surrounding powder insulation. This adjustment

may result In lowering the NBS values by about one- third percent at 0°C

and about one percent at 600°C. Aside from this correction, uncertainties

In the results given are estimated to be about one percent.
, .

-

-

V

•r« I fl
THERMAL

CONDUCTIVITY

,

wott/cm-degC

DEPARTURE

%t

-200 -100 0 100 200 S 00 400 500 600 700

TEMPERATURE ,

FIGURE 1„ THERMAL CONDUCTIVITY OF ARMCO IRON (SAMPLE

SUPPLIED BY BATTELLE MEMORIAL INSTITUTE)

THE UPPER DRAWING SHOWS THE DEPARTURES OF

THE NPL RESULTS FROM THOSE OBTAINED AT NBS

- 6 -

Electrical resistivity measurements have been made from liquid nitrogen temperatures to room temperature, and are in good agreement with the

results of Powell [ 3 ] over this range. High temperature electrical re- sistivity measurements on a sample of Battelle Armco will be made soon..

3.- LEAD

Van Du sen and Shelton [7] selected lead as the primary standard for

their comparative method of thermal conductivity measurement. At the time,

they felt that the thermal conductivity of lead was known within 3 percent

or better at the ice point, and assumed the value to be 0.352 watt/cxn deg G

at O^C, as given in the International Critical Tables. They determined the

temperature coefficient (to 3 00°C) as 0.057 percent decrease per degree C.

Since that time, several investigators [8,9,10,11,12] have either used lead

as a primary standard in a comparative apparatus, or have checked their

equipment using lead.

In view of the continued use of lead as a thermal conductivity reference standard, it was decided to survey the .literature to determine the

need for a new absolute measurement of the thermal conductivity of lead.

The curve in the lower drawing in Figure 2 shows values wT e have deduced

from the literature for the thermal conductivity of lead as a function of

temperature. The values plotted are listed in Table 2.

DEDUCED THERMAL

TABLE 2

•

CONDUCTIVITY OF LEAD

Temperature 0 k

-250*0 0.484 w/cm C

-200 .402

-100 .368

0 .352

100 .336

200 -320

300 .305

These values were obtained by fairing a curve through the available literature data over the temperature range from -250° to 30$°C. The percent
I
THERMAL

CONDUCTIVITY

,

w/cmC

DEPARTURE

-7-

- 200 -100 0 100 EOO 000

TEMPERATURE *C

FIGURE 2^ DEDUCED VALUES FOR THE THERMAL CONDUCTIVITY OF

' LEAD. THE UPPER DRAWING SHOWS DEPARTURES OF DATA

OF VARIOUS INVESTIGATORS FROM THE DEDUCED VALUES

A. Lorenz (13) T Konno (21)

BJaeger & Van Du sen &

Diesselhorst (14) Shelton (7)

C. Macchia (15) • L* Brensue r &

D* Lees (16) da Haas (23)

Meissner (17) M. Scholes (8)

F o Schott v.iU) N. Weeks &

G. Peczalski (19) Seifert (9)

Ha King (20) . 0. Franc 1 &

i. Bidwell & Ki'ngery (10)

Lewis (22)

departures of the individual investigations [ 13*14*15*16, 17, IS, 19,20*21*22*

7 y 23 * 8*9*10] from this smooth curve are shewn in the upper drawing in Figure

2» The construction of the smooth curve ohown in the lower drawing was

somewhat arbitrary* in that the investigations indicated .by solid lines in

the upper drawing were given heavier weight than those indicated by broken

lines « Owe literature reference [24] was found subsequent to the Ottawa

meeting and is not included in Figure 2. •

In searching the literature a number of other references [25*26*27*28*

23 .30 *3!,32>33 *34*35*36] ware found which gave data at temperatures below • **250°C|- these data were not Included la the present survey* but the references are given for the cake of completeness

Inspection .of Figure 2 reveals that all data except those of three

investigations [15»18*19] appear to indicate a conductivity at 0°C within

About 2 percent of- the j deduced value for G

UGI At both lower and higher

teiioeratures* the various data diverge markedly* It is 'estimated, that the

uncertainty of the values given in Table 2 is about 2 percent at G^C* but

increases to about 5 percent at -210 VC .and at ^OO^G* Because there is uncertainty as to the purity ©£ the leads used in come of the investigations

the value's in Table 2 are not considered to establish a bent line for pure

lead*

The national Bureau of Standards has recently issued a' new lot of - freezing point lead (Standard Sample 49a $ the freezing point is 3 27, 41

±0*005 degree) * The same lead might also prove useful as a thermal conductivity standard* The Heat Transfer Section has obtained a sufficient

quantity of this lead to fabricate a specimen for the BBS metals apparatus.

Vie. 'plan* as soon as the work load permits* to measure both the thermal conductivity and the electrical resistivity of this lead from about -*160* t© . 250^0*

4* IKQOttgL 702 •

In order to ebtdiss idle highest pg^aible . accuracy in: comparative thseaal

conductivity meaaureiihht© $ it Is desirable to have a reference material

having a thermal co'M'aeti^ity appsaKimitaly similar to that ©f the test

specimen materials* th i^iew of the current importance of heat resistant

alloya such as st&inleip. 43d nickel-chromium alloys* a reference

material of this type appear to ba quite useful, Powell and Tye 157]

have suggested the use &$ G steel” as a thermal conductivity standard

end have measured the thermal . and electrical ’conductivity of this material

<43*75% Fa^, 30® 5% Mi* 16*75% Cr) over the temperature range 0* to 8O0 DC*

In another recent paper [ 38 ]* -the same authors reported thermal and electrical conductivities for a number of similar nickel-chromium alloys* It can
.
~Q

be seen from the data given in these two papers that the thermal conductivity of these highly alloyed materials is relatively insensitive to minor

changes in composition. Furthermore , there is good correlation between

thermal and electrical conductivity.

A few years ago, the KBS Heat Transfer Section procured a stock of

Inconel 702, which was chosen because of its excellent oxidation resistance

at temperatures up to 130Q°C, An NBS chemical analysis gave the following

composition, in weight percent; Hi 79.3 * Cr 17.0, A1 2.5, Ti 0.59, Fe O .36

Si 6.19, Cu 0.14, Co 0.08, Mn 0.04, C 0.066, P 0.002, S 0.004. The Inconel

702 stock obtained by NBS was in a solution-annealed condition (i.e., had

been held at 1080 °C for one hour followed by rapid air cooling) when re- ceived from the suppliers. If held at temperatures between about 650° and

900 °C, this alloy will become age-hardened due to precipitation of particles from the solid 'solution.

The thermal conductivity of specimens fabricated from this lot of Inconel 702 has been measured at NBS by three different methods, using five

different apparatus. The results obtained have been used to deduce probable values for the thermal conductivity of this alloy in both the solutionannealed and the age-hardened condition. The values obtained are listed in

Table 3 • Above about SOO^C, the thermal conductivity of this alloy is relatively independent of thermal history and a single column is given.

TABLE 3

THERMAL CONDUCTIVITY OF INCONEL 702

Temperature Solution- annealed Age-hardened

. -150°C 0,099 w/cm C

-100 - 103 -----

0 . 114

100 . 127

200 . 141 0.145 w/cm C

300 . 158 .162

400 . 176 .179

500 . 195 ,198

600 ,216 , 2 x 8

700 rp .239

800 0 . 259

900 ,281

1000 .301

1100 ,321

1200 .340
. . - .... f. - v-' • '•
- 10 -

The thermal conductivity of solution- annealed Inconel 702 is shown

plotted against temperature in the lower drawing of Figure 3 * In the upper

drawing, the smoothed results obtained in each of the several apparatus are

shown as departures from the curve in the lower drawing. The solid curves

refer to solution-annealed metal below 65Q°C; the broken curves refer to * metal which had been age-hardened. The curve labeled M represents manually

smoothed data from numerous runs on two specimens in two models of the NBS

metals apparatus [5,6]. The curve labeled P corresponds to a quadratic

equation of least-mean-squares fit to the data obtained in an early model

of the NBS absolute cut-bar apparatus [55] on a specimen 2.54 cm in diameter

and 3«S1 cm long. The curve labeled A corresponds to the cubic equation of

least-mean- squares fit to the data obtained in the NBS high temperature absolute cut-bar apparatus [57] on a specimen 2.54 cm in diameter and 6.59 cm

long. The curve labeled A* corresponds to the cubic equation of least mean

squares fit to the data obtained in the NBS high temperature absolute cutbar apparatus on the same specimen as wa3 used for curve A, which had become age-hardened in the apparatus at the higher temperatures of curve A.

The specimen was not disturbed between these sets of tests. The curve

labeled S corresponds to the linear equation of least-mean-squares fit to

the data obtained in the NBS steam calorimeter apparatus on an age-hardened

specimen 15.2 cm in diameter and 2,54 cm thick.

It can be seen in Figure 3 that all of the smoothed results obtained

for the solution-annealed alloy to SOO^G (M,P,A) are within plus or minus

one percent of the values given in column two of Table 3* The thermal con- ductivity -values obtained in the high temperature absolute cut-bar apparatus for the age-hardened alloy (curve A

! ) should be quite good relative to

values obtained in the same apparatus on the same specimen in the solutionannealed condition. The divergence of curve S from curve A' is believed to

be due to inaccuracies in the data obtained using the steam calorimeter apparatus (1 . e, , curve S is believed to be in error). We plan to measure the

thermal conductivity of an age-hardened specimen in the NBS metals apparatus.

Electrical resistivity measurements have been made on solution- annealed

Inconel 702 from -195° to 30Q a C. Powell and Tye [ 38 ] found that the thermal

conductivity of a group of nickel -chromium alloys could be predicted within

5 percent or better over the- temperature range from 50 & to 800 c C by means

of the equation

k

1 = 2.2x10"

8

(T/p) * 0,060 (1)

where k

} is the predicted thermal conductivity (w/cm C) , T is the absolute

temperature (°K), and p is the electrical conductivity (ohm- cm) . Using the

electrical resistivity values measured, equation ( 1 ) was used to calculate
'

-

-

' •
THERMAL

CONDUCTIVITY

,

vv/cm

deg

-ii-

-200 0 200 400 600 600 1000 1200 1400

TEMPERATURE ,°C

FIGURE 3. THERMAL CONDUCTIVITY OF INCONEL 702 IN THE

SOLUTION-ANNEALED CONDITION (M,P*A) AND IN

THE AGE- HARDENED CONDITION (A',S). THE

UPPER DRAWING SHOWS DEPARTURES OF THE

SMOOTHED RESULTS OBTAINED IN SEVERAL.

APPARATUS

M - Metals apparatus

P - Prototype absolute cut-bar apparatus

A,A' - High' temperature absolute cut-bar

apparatus

S - Steam calorimeter apparatus

- 12-

thermal . conductivity values for solution-annealed Inconel 702. Table 4 presents the measured values for electrical resistivity, p, and thermal conductivity, k, the calculated thermal conductivity values, k

1 , and the percent

departure, 10Q(k’-k)/k, of the calculated values from the measured values,

and the Lorentz function kp/T, from -150°C to 300°C

TABLE 4

CORRELATION BETWEEN THERMAL CONDUCTIVITY AND

ELECTRICAL RESISTIVITY OF SOLUTION ANNEALED INCONEL 702

t 0 k k' <=> O 1 ko/T

°c w/cm C w/ cm C: % v

2 /deg2

-150 122.7 0.099 0.080 -19 9.86x10

" 8

-100 123.9 . 103 .091 -12 7.37

0 125.8 .114 .108 -5 5.25

100 - 127.0 .127 .125 -2 4.32

200 127.8 .141 .141 0 3. 81

p 00 128.5 .158 .158 0 3.54

In the temperature range for which it was intended. Powell and Tye's

equation is seen to hold very well At lower temperatures, the calculated

values depar t signifi cantly from the cbs erved values. This is not sur- prising, esp ecialiy in view of the; very high values obtained for the Lorentz

function (the theoretical value fo r elec tronie conduction is 2.443xl0“ 8

volt2/deg2X) 6 We intend to measure the electrical resistivity of Inconel 702 up to

at least 12Q0°C, with particular attention to the effects of heat treatment.

Samples of this alloy (cut from the same plate as were the NBS specimens)

have been sent to Dr. R. W» Powell of the National Physical Laboratory

(Teddingtori, Middlesex, England) , to Dr. M. J. Laubitz of the National Research Council (Ottawa, Ontario, Canada), to Dr.-Ing, Karl-Heinz Bode of

the Physikalisch-Technische Bundesanstalt (Braunschweig, West Germany)

,

and to several laboratories in the United States. In conjunction with

thermal conductivity measurements, many of these laboratories will also

make electrical resistivity determinations.

PYROCERAM CODS 9606

Measurements have bean mads of the thermal conductivity of a '•microcrystalline glass (Pyroceram 9606, product of Corning Glass Works, Corning

New York)* Microcrystailine glass is first formed as a homogeneous glass

(incorporating a nucleating agent) which is transparent, so that any defects can be readily detected visually. By suitable heat treatment, the

glass is later converted (by Coming) to a polycrystalline solid, which is

opaque as a result of the large number of very small crystals. The proper

ties of such materials have been described in the literature [39,40],

Measurements have been made in the N3S high temperature absolute cutbar apparatus [57] on a specimen in the form of a cylinder 2,540 cm in diameter and 1*269 cm in length* The density of the specimen material was

2,601 g/cm° (value supplied by Coming). The thermal resistivity of

pyracetam Cede 9606 was found .to increase linearly from 200° to XG00 ft C,

and can be represented by the equation

w = 1/k = 26.7 + S.7 (“qqq) ( 2)

with a standard deviation of less than one percent, where w is thermal re- sistivity (cm deg C/watt) , k is thermal conductivity (watt/cm deg C) , and

T is temperature (°C). Thermal conductivity and resistivity values calculated from equation (2) are shown in Figure 4 and are listed in Table 5,

THERMAI

RESISTIVITY

TABLE 5

i CONDUCTIVITY AND

OF PYROCERAM CODE 9606

T k w

w/cm C cm C/w

20 0 0

,

03 DO 28,6

400 * Co 27 30.6

600 .0303 32,5

800 .0290 34.5

1000 « 0275 36,4

-14-

FIGURE 4« THERMAL CONDUCTIVITY AND THERMAL RESISTIVITY

OF PYROCERAM CODE 9606 MICROCRYSTALLINE GLASS

THERMAL

RESISTIVITY,

cm-deg

C/watt

- LDThe specimen was held at lOOO^C for about 275 hours; data taken after

this extended heat treatment were in substantial agreement with those taken

before the specimen was held at 1000°C, thus indicating that no appreciable

change in the thermal conductivity of Pyroceram 9606 occurred as a result

of this heat treatment.

Measurements on Pyroceram 9606 have also been made in the NBS metals

apparatus over the range 100° to 650°C. The data have not been completely

analyzed, but appear to be in good agreement with the values obtained in

the high temperature absolute cut-bar apparatus. Thermal diffusivity

values for Pyroceram Code 9606 have been reported by Plummer, Campbell,

and Comstock [41]. Thermal diffusivity measurements are also being made

by Ho W. Flieger and D. C. Ginnings of the NBS Heat Measurements Section.

I 6. PYREX GLASS

The thermal conductivity of Pyrex glass has been measured by numerous

investigators, and this material has been used for calibration or checking

of thermal conductivity apparatus. The NBS Heat Transfer Section has measured the thermal conductivity of Pyrex Code 7740 in the NBS guarded hot

plate apparatus and in an early model of the NBS absolute cut-bar apparatus.

This glass was found to have a density of 2,2258 g/cm3

at 24.3°C. For

further identification, the refractive index w7as measured at 23°C and found

to be 1 . 47257±0 o 00003 for the D lines of sodium (5893A), In the course of

determining the index of refraction, it was noted that the glass prism (prepared from polished Pyrex plate) was somewhat strained. After annealing,

the index of refraction was found to have decreased to a value- of 1.47211

±0 /00003 . Thermal conductivity specimens were not annealed prior to

me as ur ement

The NBS results were used, in conjunction with literature values and

several unpublished data available to us from other laboratories, to deduce probable values for the thermal conductivity of Pyrex glass. The

values arrived at are given in Table 6 and are shown plotted in the lower

curve of Figure 5.

The various determinations [42,44,

of the thermal conductivity of Pyrex gl

of Figure 5 as percent departures from

Two references [43,46] were excluded as

45,47,48 and 49,50,51,52,53,54,55]

ass are shown in the upper drawing

the smooth curve in the lower draw in

being outside the range of the

drawing* One reference [41 ] was received too late to be included. It is

very doubtful that the scatter seen would be due to differences in chemical

composition [41,56], Differences in the microstructure could be responsible [41] for some of the observed differences. but most of these must be
• -V •• * •• I I B I*
-16-

attributed to experimental errors. It is estimated that the derived values

are given in Table 6 are uncertain by not more than 5 percent below 30G°C.

Above this temperature, radiation affects cause the thermal conductivity

to become a somewhat ambiguous property. We plan to make additional measurements of the thermal conductivity of Pyrex Code 7740 glass.

TABLE 6

DEDUCED VALUES FOR THE

THERMAL CONDUCTIVITY OF PYREX GLASS

Temperature Thermal Conductivity

tip watt/cm deg C

0 0.0111

so .0116

100 .0122

150 .0127

200 .0133

230 | .0138

300 .0143

400 (0.0154)

500 (0.0165)

-1

FIGURE 5„ DEDUCED VALUES FOR THE THERMAL CONDUCTIVITY OF

PYREX GLASS 0 THE UPPER DRAWING SHOWS DEPARTURES

OF DATA OF VARIOUS INVESTIGATORS FROM THE DEDUCED

VALUES

B Bridgman (42)

S Stephens (44)

BC Birch & Clark (45)

L Lucks , Deem &. Wood (47)

K Kingery (48' & 49)

C Chai loner, Gundry &

Powell (50)

X Laboratory X (51)

Y Laboratory Y (52)

Z Laboratory Z (55)

W Watson (54)

F Flynn (55)

-18-

[ 1 ]

[ 2 ]

bl

[4]

[5]

[ 6 ]

[7]

t3]

[9]

[ 10 ]

[ 11 ]

[ 12 ]

7. REFERENCES

Robinson, H. E. , "Thermal Conductivity Reference Standards," NBS

Report 7835.

Powell, R. W. , "Armco Iron as a Thermal Conductivity Standard, Part

I: Review of Published Data," Progress in International Research on

Thermodynamics and Transport Properties, ASMS, Academic Press,

New York (1962)

Powell, R. W. , "Armco Iron as a Thermal Conductivity Standard, Part

II: New Determinations at the National Physical Laboratory," Progress in International Research on Thermodynamics and Transport

Properties, ASME, Academic Press, New York (1962).

I Laubitz, M. J«, "Thermal and Electrical Properties of Armco Iron at

High Temperatures," 'Can. J. Phys. , £8 (I960), pp 887-907.

Watson, T. W. and Robinson, H. E. , "Thermal Conductivity of Some

Commercial Iron-Nickel Alloys," Trans. ASME J. Heat Transfer (Nov.

1961), pp 403-408.

To be published; the NBS high temperature apparatus is essentially

similar to the low temperature apparatus [5] but is constructed of

more refractory materials.

Van Dusen, M. S. and Shelton, S. M. , "Apparatus for Measuring

Thermal Conductivity of Metals up to 60G°C," J. Research NBS 12 , RP 668 (1934), pp 429-440.

Scholes, W. A., "Thermal Conductivity of Bodies of High BeO Content,"

J. Amer0 Ceram. See. 33 [4] (1950), pp 111-117.

Weeks, j'. L. and Seifert, R. L. , "Note on the Thermal Conductivity

of Synthetic Sapphire," J. Amer. Ceram. Soc. 35 [l] (1952), p 15.

Fraud, J. and Kingery, W. D. , "Thermal Conductivity: IV, Apparatus

for Determining Thermal Conductivity by a Comparative Method," J.

Amer. Ceram. Soc. 3Z [2], Part II (1954), pp 80-34.

Silverman, L. , "Thermal. Conductivity Presented for Soma Metals and

Alloys up to 900^0," J. Metals j5 (1953), pp 63 I- 632 . Lucks, C. F. and Deem, H. W. , "Thermal Properties of Thirteen Metals,"

Amer. Soc. for Testing Materials Special Technical Publication 227

(1958)

/
I
-19-

r yz 1

L J

[14]

[15]

[16]

[ 21 ]

[ 22 ]

[ 23 ]

1.24]

[253

Lorenz, L* , "(fiber das Leitungsvernznogen der Metalle fur Warme und

Eleccricitat ," Ann, Physik 15 (1381) , pp 422-447 and 582-606.

Jaeger, W. and Diesselhorst , E* * "Warmeleitung, Elektricitatsleitung,

Warmecapaeitat und Thermokraft einiger Metalle," Miss* Abhandlung

Phys. Techn, Reichanstalt 2 (1900), pp 269-424 (cataloged under

Charlottenburg)

Macchia, P., "Ricerche Ulteriori sopra la Conducibilita Termica a Basse Temperature," Accad, Lincei, Atti, 16. (1907), pp 507-517,

Lees, K, , "The Effects of Temperature and Pressure on the Thermal

Conductivities of Solids - Part 2. The Effects of Temperature on the

Thermal and Electrical Conductivities of Certain Approximately Pure

Metals and Alloys," Phil, Trans* Roy, Soe„ (London), A208 (1908),

pp 331-443-

[17] Meissner * W. * "Thermische und Elektrische Leitfahigkeit einiger Metalle

[13]

[19] Peczalski* T. * "Contribution a l

1 etude de la Conductabilite Calorificue

[ 20 ]

Zwischen 20 und 373^ Abs*” Aim* Physik 47 (1915), pp 1001-1058,

Schott, R. , "Uber das WarmleItVerrrJb'gen einigen Metalle bei Tiefen

Temperaturen

,

1 ’ Verhand* Deutsch* Physik, Gesell, 18 (1916), pp 27-3-4,

des Solides," Ann, Physique 2 (1917), pp 185-224-

King, -R, W», "Measurement of Heat Conductivities of Metals at High

Temperatures," Phys, Rev, JQ (1918), pp 149-150,

KorniOj J, , "On The Variation of Thermal Conductivity Luring the

Fusion of Metals," Science Reports of the Tohoku Imperial University,

First Series (Sendai, Japan), JS (1919), pp 169-179 (cataloged under

Sendai)

Bidwell, C* C, and Lewis, E. J* , "Thermal Conductivity of Lead and

of Single and Poly Crystal Zinc," Phys, Rev. 33 (1929) , pp 249-251,

Bremmer, H, and de Haas, W. J, , "On the Conduction of Heat by Some

Metals at Low Temperatures," Physica £ (193*8), pp 672-686,

Bidwell, C, C., "Thermal Conductivity cf Metals," Phys, Rev- 5S

(1940), pp 561-564.

de Haas, W. J, and Bremmer, H, , "Thermal Conductivity of Lead and

Tin at Low Temperatures," Comm* Kamerlingh Onnes Lab. , Univ, Leiden,

19 (1931) , No, 214, pp 37-52,
**
[26] Mendels a ohn s I<« and I^ontiua, XL B 0 , "Thermal Conductivity of Supraconductors in a Magnetic Field,” Phil. Mag« 24 (1937) , pp 777-787*

[27J da HaaSn 17.® J* and Bademakers , A* $ "The Thermal Conductivity of Lc.cd

in the Superconducting and Kormal State,” Physica 7 (1940) s pp 992-

1002 ,

[ 2Sj irdd croakers , A®, "Tha Thermal Conductivity of Lead and Tin in the

Superconducting and in the BoraaX State,” Fhyglea 15 (1949), pp 849-

859,

[29] Mendelssohn, XL and Essenberg, i-L M* , "The Thermal Conductivity of

Metals at Low Temperatures II t The Transition Elements,” Proc. Phys*

Soe* (London), A6 S (1952), pp 388*354.®

[pO ] Olsen, J* L® a "Heat Transport In Lead-Bismuth Alloys,” Pros. Phys.

See* A65 (1952) s pp 518-532®

[31.3 Olsen, J® L® and Eantou, C* A* , "Heat Conductivity of Superconductive

Lead Below 1%” Phil, Mag, 43 (1952), pp 946-948,

[ 32 ] Mendelssohn, XL and Rosenberg, Eh M® s "The Thermal Conductivity of

Metals in High Magnetic Fields at Low Temperatures,” Proc* Roy, Soc.

(London) , A21S (1935) » PP 190-2BS*

[33i Olsen, J« Lev and Rosenberg,- XL M# , "The Thermal Conductivity of

Metals at Low Temperatures," Adv.® Physics 2 (1953)

pp 28-65,

[54] Rosenberg, XL M* , "The Thermal Conductivity of Metals at Low Temperatures,” Phil, Trans » Roy, Soc® (Loudon) , A24

(1955) , pp 441“

497,

[35] Montgomery , H* , "The Thermal Conductivity of Lead at Low Temperatures,” Proc® Roy® Soc® (London) , A244 (1958), pp 85-100®

[38 ] Rowell, F® M«, "The Thermal Conductivity of Some. Superconductors,”

Free® Roy® Soc® (London), 1254 (1960), pp 542-550®

[ 37 ] Powell, R« W®, and Tys, R« P® , "High Alloy Steels for Use as a

Thermal Conductivity Standard,” Brit® Jour® of Appl® Phys® Mi [5],

Lee: don (I960), pp- 195*198®

[ 38 ] Powell, 2L W® and Tye, XL P® , "Eisrmtl and Electrical Conductivities

of Hiskel-Chrcmiisa (Mimonic) Alleys,” The Engineer (1960) , pp 729-

732®

-21 -

[ 39 ]

[40]

[41 j

'‘Glass Ceramics Chexn. Eng, News 39 (June 19, 1961),

Stcokey, S, I),, "Glass Ceramics," Mech. Eng . 82 (Oct. I960), pp 65-68

Stookey s S. B.

,

pp 116-125.

Plummer, W. A., Campbell, X>* E. } and Comstock, A. A., "Method of Measurement of Thermal Biffu3ivity to lOGO^C," J. Amer. Ceram. Soc. 45

(1962), pp 310-316.

Several Nocks Under High Pressures," Am, J. Sci. J7 (1924), pp 81-102.

Reulos, R. , "Method for the Measurement of the Thermal Conductivity

of Glasses," Rev. d'Optique 10 (19pl), pp 266-272.

Stephens, rJ ¥. "The Temperature Variation of the Thermal Conductivity of Pyrex Glass," Phil* Mag. _14 (1932) , pp 897-914.

[42] Bridgman* P. W, , "The Thermal Conductivity and Compressibility of

[43]

[44]

[45] Birch, F. and Clark* H* , "The Thermal Conductivity of Rocks and its

Dependence upon Temperature and Composition," Amer. J. Sci. 258

(1940), pp 529-558.

[46] Knapp, ¥. J. , "Thermal Conductivity of Non-Metal lie Single Crystals " J. Am. Ceram. Soc. 26 £ 2 J (1943), pp 48-55.

[47 j Lucks s C. Deem, H. W. , and Wood, ¥. D. , "Thermal Properties of

Six Glasses and Two Graphites," Amer . Ceram. Soc, Bull. 39, (I960),

pp 3 13 “3 19

[48] Kingery, W. X). , "Thermal Conductivity i XIV, Conductivity of Multicomponent Systems*" J, Amer. Ceram. See. 42 [12] (1959), pp 617-627

[49] Kingery, W. D. , "Heat Conductivity Processes in Glass," J. Amer.

Ceram. See. 44 (1981)* pp 302-364

[30] Challcner, A* R. , Gundry, lu A„ ,

, Flow Apparatus for Liquid Thermal

• Proc. Roye Soc. A245 (1958), pp 2.

[51] Private communication free& eabora'

guarded hot-plate apparatus

[52] Private communication from laboratory Yj determination made using

[[l i* -S ^ *» U Cii. .

[531 Unpublished data from laboratory Z,

22-

[54] Kate T. W. , 'private Cfflaanmieatienj Baaeureaent aade using the KBS

guarded hot plate apparatus©

reel b« R. and Robinson, H. E. , "Thermal Conductivity of Setsi1 " — _M-t‘f ve Solids | Method for Steady-State’ Measurements on Small

Di'sc^Reference Samples - Interim Technical Report Covering Period

_ February 23 $ 1959 to March 31 » 1961, 88 MBS Report 7 i35, Apr^X uo,

1901©

" ‘

’

• .

r rg*; cliffe E© H« * "Preliminary Measurements to Determine the Effect

0£ sition on the Thermal Conductivity of Glass,”. Phyc* and Chem*

Glasses JL (1960), pp 103-1C-4*

r 57 *[ R.« "Thermal Conductivity of Semiconductive Solids; Method

for ttuniv-State Measurements ca Email Disk Reference Samples

• Interim Technical Report Covering Period April 1, 1961 to August .pi,

1962 MBS Report 7740, October 29, 1962©