A HIGH TEMPERATURE THERMOMETER

BY SYLVESTER BOYER

ABSTRACT

High Temperature Thermometers. The thermometer resembles that of the mercury in glasstype but is graduated to 10000C. It uses fused quartz as the container and the rare metalgallium as the filling liquid.

The paper includes a brief description of the Properties of Gallium with reference to itsuse in thermometers. Gallium is the only metal with a low melting point (29.70 C) and highboiling point (1500-2000'C). Together with these unusual properties and that of under-cooling (-20'C or below) which makes it an ideal thermometric liquid if it were not for thetendency to wet glass and quartz surfaces.

The experimental investigation recounts the method for overcoming the wetting propertywhereby additional information was obtained on the properties of gas solution; surfaceoxidation, undercooling of liquid gallium and the effect of impurities on increasing the wettingproperty.

The filling operation in preparing the thermometer and the successful method of etchingquartz and marking the graduations are briefly described.

The new thermometer resembles that of the well known mercurythermometer. But unlike the latter its upper limit is about 1000'C,500TC being that of the mercury in glass instrument. It utilizes fusedquartz as the container and in place of mercury the rare metal gallium.The suitability of fused quartz for a thermometric container has longbeen known. Professor Elihu Thomson pointed out this applicationtwenty-five years ago. The suitability of fused quartz for thermometersis due to its clearness, lack of hysteresis compared to glass, smallcoefficient of expansion and its high melting point.

Although gallium possesses certain properties, such as high boilingpoint, very necessary for its use in high temperature thermometers, itsproperty of wetting vitreous substances, such as glass and quartz, hashitherto prohibited its use for this purpose. This deficiency was pointedout by Lecoq-de Boisbaudran soon after its discovery in 1876.

Scientific laboratories have felt a need in the past for an accuratetemperature measuring device because thermocouples are inconvenientand unreliable for those not especially accustomed to their uses. Such atemperature measuring device has also been needed in commercialindustries because pyrometers must be frequently recalibrated. Evenin the upper limits of the glass thermometers the high pressure requiredto raise the boiling point of the mercury enhances the hysteresis ofthe glass which makes these thermometers especially inaccurate overthe 350-500C range.

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[J.O.S.A. & R.S.I., 13

* This need for an accurate high temperature measuring device couldnot be supplied for lack of a suitable metal with a high boiling pointwhich will flow through a capillary tube without wetting or tailingbetween temperatures of 0C and 1000C.

The first problem, therefore, was the preparation of a suitable fillingliquid. Such a liquid must remain liquid at 0C or below, have a highboiling point, not attack the container at 10000C and must flow freelythrough capillary tubes without tailing or the thread breaking.

PREVIOUS WORK ON FILLING LIQUIDS

Mercury in quartz thermometers (graduated to 7500) have been madein Germany in limited numbers, the boiling point of mercury beingraised by using gas at high pressure within the tube. The thermometerhad to be jacketed giving the appearance of the known Beckman type.

Dufour' realizing the limits of mercury for high temperature measure-ments attempted to substitute tin as the filling liquid but he was notsuccessful. The emergent thread of molten metal no doubt solidifiedin the stem which fractured the bulb when further expanding. Thewriter has found that the metal, which has a melting point above75-90C, will not be heated by conduction sufficiently through theprojecting metal thread to maintain it in the liquid state. (Obviouslya number of variable factors affect the exact temperature at the top ofthe emergent thread, such as the temperature of the room and the aircurrents.)

Sodium-potassium alloys have been tested as substitutes for mercurybecause of their relatively high boiling points. But because they arealmost impossible to manipulate without becoming surface oxidized,they always thereby wetted the quartz because of the reaction of theseoxides with the quartz at elevated temperatures.

The writer some years ago undertook a research2 concerning thedifficult problem of the purification of gallium and the determinationof some of its physical and chemical properties. During this investiga-tion the basic preparation was made for the present development. Itwas observed that some of the properties of gallium depend on thetreatment. More recent investigations in this laboratory on the possiblecommercial applications of gallium have verified the earlier conclusionsand have demonstrated the suitability of gallium as a thermometricliquid. The wetting of glass and quartz surfaces by liquid gallium which,

1 High Temperature Measurements, p. 365, 1911, by Burgess Le-Chatelier.2 Richards and Boyer, J. Amer. Chem. Soc., 43, p. 274; 1921.

118 SYLVESTER BOYER

HIGH TEMPERATURE THERMOMETER

as noted above, had prohibited its use as a thermometric liquid, wasfound to depend on the gas pressure above the metal, the purity of themetal, surface oxides, water films, and absorbed or dissolved gases.This paper briefly recounts these experimental observations. But beforebeginning this description a number of the properties of gallium will berecounted.

PROPERTIES OF GALLIUM

Gallium is one of the rare metals occurring in the third group of theperiodic table of the elements. Thus it resembles aluminum and indiumin some of its properties. Like aluminum and indium it has a highboiling point, about 1700'C but unlike aluminum which melts at 6570C,it melts at 29.70C. Indium melts at 155C. Lecoq observed thatgallium may be undercooled to 1 or- 20C before solidification if care wastaken to avoid the addition of a crystal of the solid.

Both pure and impure gallium expand3 upon solidification.Like aluminum, a thin layer of surface oxide readily forms which

protects the metal from further oxidation. The first observers concludedthat gallium was not subject to such oxidation. Subsequently, measure-ments of surface tension by the, flat drop method indicated surfaceoxidation in spite of laborous efforts to avoid it.

Lockyer4 observed that no gas was evolved upon heating in vacuo.On the contrary,5 others have observed that bubbles of gas were evolvedwhen the solid metal was immersed in hot water.

Gallium readily reacts with the halogen gases or with the correspond-ing acids, forming salts. Among these the chlorides are formed mosteasily. The dichloride melts at 1640C and boils at 5350C. The tri-chloride melts at 75.50C and boils at 210-215C.

Recent work on gallium in this laboratory has added to the generalknowledge concerning the following properties:

(1) Gallium when highly purified and sealed in quartz tubes under2-5 microns pressure could be undercooled often to -20'C withoutbecoming solid. But in the presence of mere traces of bismuth theamount of undercooling was lessened and often at room temperaturethe liquid would solidify. Certain impurities in appreciable quantitiessuch as tin and indium did not affect this property of undercooling.Traces of zinc had but little effect. The effect of larger quantities is

Richards and Boyer, 43, p. 274; 1921.Chemical News, 43, p. 101; 1879.

5 Lecoq and Jungfleisch Bull. Soc. Chim., (2), 31, p. 50; 1879.

July, 1926] 119

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120 SYLVESTER BOYER [J.O.S.A. & R.S.I., 1 -

not known since most zinc was volatilized under vacuum and removed

before filling the thermometer.(2) The tendency for surface oxidation was very visible when filling

the thermometer. The degree of surface oxidation was found greater

than is reported in the current literature. The tendency toward oxida-

tion increased the tendency for wetting quartz, films, scarcely per-

ceptible, making impossible the use of the metal for the thermometricliquid. Thus the metal during manipulation had to be completely

protected from surface oxidation. Use was made of the reaction between

surface oxides of gallium and warm hydrochloric acid. A thin film of

chlorides protected gallium from further oxidation until it was placed

in vacuo, after which the surface compounds were volatilized and

gallium assumed the appearance of a globule of mercury. The usual

method of removing and preventing oxidation in an atmosphere of

hydrogen was found prohibitive because gallium absorbs or dissolves

gases which were difficult to remove completely when the thermometerwas being filled.

(3) Additional facts pointing toward the evolution of gas were

brought to light during the conditioning of gallium for a thermometricliquid. One of the most difficult factors to control during the production

of the thermometer was that of complete removal of gas from the metal.

Since the metal used in this investigation was deposited electrolytically

from acid solution, it contained hydrogen. In order to remove the gas

a large drop of metal was placed in a quartz container, held under

vacuum of 2-5 microns for several hours and repeatedly heated to

1000'-11000C and cooled to room temperature until no more gas

bubbles appeared between the surfaces of the metal and the walls of

the container. During this process it was observed that upon coolingto 400-500C a large gas bubble would first appear and when the metal

was heated to 10000C the gas bubble would again go into solution,

indicating that hydrogen is more soluble at temperatures above

400-500TC. The bubbles of gas appeared to be hydrogen since they did

not tarnish the heated metal as oxygen did.Argon in the presence of gallium was much more difficult to remove

than hydrogen. Its liberation took place at a lower temperature and

in much larger quantities.The removal of gas from gallium also added to the brilliancy of its

surface and seemed to lessen the ease toward surface oxidation.

(4) The effect of metal impurities on gallium toward wetting quartz

was also investigated. As is well known impurities in mercury increases

Jkuly, 19261121HIGH TEMPERATURE THERMOMETER

its tendency for wetting glass. A similar behavior was anticipated for

gallium. The impure gallium contained indium, zinc and lead and traces

of germanium, arseric and bismuth. Lead, indium and bismuth, when

added to pure gallium, did not increase the tendency for wetting

quartz. But zinc did, as was expected. The effect of arsenic is uncertain.

All but traces of zinc and arsenic were removed during the heat treat-

ment of gallium under vacuum during the filling process. The electro-

lytic method was used for freeing gallium from its principal impurities.

The exact procedure reported previously6 was used

and found very effective.

METHOD FOR FILLING CONTAINER

The process developed for filling the thermometer

consisted briefly as follows: The metal was freed from

oxide by treatment with hydrochloric acid. When the

surface became bright, it was solidified under the acid

and the excess acid removed from the surface with filter

paper. The surface chlorides thus formed protected

the metal during transference to the vacuum appara- .

tus. When the metal was finally heated, after a good

vacuum had been obtained, the surface coating was

volatilized and the metal surface became very bright.

The metal then assumed the appearance of a globule

of mercury. The purified gallium was then introduced

into the thermometer from the pre-treatment cham-

ber. (Fig. 1.) (a) The gas bubbles formed when the

metal came in contact with the quartz, were finally

removed to a chamber (b) containing the reserve

metal. This chamber was sealed off from the ther-

mometer at (c) after the thread was set. The time of

evacuation, temperature and duration of heating were

variable, depending upon the previous history of the

metal. In order to obtain a successful thermometer

the metal had to be oxide free, gas free, and free from

the volatile impurities. This has all been accomplished FI.;

and thus gallium has been transformed to an ideal FIG. 1.

liquid for high temperature thermometers. A number of these ther-

mometers have been made during the investigation and have func-

tioned very satisfactorily. Others have been loaned to various investi-

gators for further tests.6 J. Amer. Chem. Soc., 43, p. 274; 1921.

SYLVESTER BOYER [J.O.S.A. & R.S.I., 13

MARKING AND CALIBRATION

The marking and calibration of the gallium-in-quartz thermometerpresented several new and difficult problems. Quartz is very difficultto etch. With cold hydrofluoric acid the total surface was finallyattacked since the usual protective coatings for glass did not protectin case of quartz because of the tendency to dissolve at the sides aswell as downward. Hot dilute hydrofluoric is better in this respect.It was, therefore, necessary to find a coating of sufficient protectiveproperties at 90'C-100 0 C. Polymerized china wood oil adequatelyserved the purpose. Hot dilute hydrofluoric acid could now be usedand the surface of the quartz was protected and the marks wererelatively sharp and deep. The etching alone is satisfactory whereaccuracy is desired for materials spread when fused in the etched marks.When greater visibility is demanded, a composition to color the etchedmarks may be used. After the usual trial samples, it was found thatsand and copper oxide in certain proportions would form a sharpgreyish-black mark which was resistant to most chemical reagents,and to heat treatment at 10000C. Thus a very satisfactory method formarking the graduations was developed.

The fixed points on the thermometer scale were determined by com-parison with a thermocouple as standard, or by direct comparison withcertain well known standards for temperature. Temperatures in therange of 700TC and above presented a greater difficulty since the ther-mometer had to be protected from the action of the metals, or thesodium chloride used and thus greater uncertainty in the accuracyof calibration was experienced.

Acknowledgments are made to Dr. Edward R. Berry for his con-tinued interest in this investigation and to Mr. Berthold Niedergesassfor the many valuable suggestions on the method of filling and the careof fused quartz.

(1) This paper includes a description of a process for overcoming thetendency of gallium for wetting quartz.

(2) A brief description of the process for filling the quartz ther-mometer and the method for marking the graduation.

THOMSON RESEARCH LABORATORY,GENERAL ELECTRIC CoMPANY,

WEST LYNN, MASS.

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