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Project Cirrus. Occasional Report Number 6

GENERAL ELECTRIC CO SCHENECTADY NY

15 OCT 1948

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Occasional Report Number 6

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01:;;\: It> ' \ : ) :1 /
1-------------t
~e
Variation with Temperature of Nucleation Rate -'--,---.-
,
-------1
I ;"";11 .J: d Or I
or:~\lpercooled Liquid Tin ~~ _Wa~er Drops
-Oist ~ I-- <'C!ul

Prepared by

Bernard Vonnegu_t

The--research reported in this· document was made possible through support exte~ded the Research
Laboratory -of the General Electric:Company joinUy by the Signal Corps and the Nayy Department (OCfice of
Naval Research) under Signal Corps'Contract No. W-36-039..,§_C-32427. Acknowledgemenqs also made of
assistan-ce from the Army Air For~es in providing aircraf~ and associated personnel;

~../2~b~
~~~
Schenectady, NeWOrk
t5 October 1948 '
·G. E. Re~isit1on

EDG~2J190

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-­
 VARIATION WITH TEMPERATURE OF THE NUCLEATION RATE
OF SUPERCOOLED LIQUID TIN AND WATER DROPS
A. rnTRODUCTION
In investigations of the kinetics of the formation
of a new _phase, it is Important to learn at what rate
nuclei, or centers oC Cormation Cor -the new phase,
make their appearance. It is possible to investigate
the rate of nucleation by observing single masses
of material during and after a phase transformation.
However, in many cases it is difficult to separate
the kinetics of nucleation from the kinetics of the
growth of the new phase after nuclei have made
their appearance. The nucleation of a substance
can often be more easily studied by dividing It Into
a large number of small, mutually independent par­
ticles and observing as afunction of time the num­
ber of particles which have undergone transCorma­
tion. The time required for a particle to change
• from one phase to another once a nucleus has formed
will, -In general, be proportional to the first power
of the particle radius. The chance that a nucleus
will form _will generally be proportional to the sec­
oild or third power of its radiUS. Therefore, by
making ~e particle sufficiently small, the time
required -for the occurrence of a _nucleus can be
made-large In relation to the timej'equlred for the
particle to transform once a nucleus-has appeared.
It Is advantageous to make nucleation-measurements
on systems containing a sufficiently large number of
particlesJo be easily treated statistically.
Preliminary investigations have been made on
the nucleation of supercooled tin _and supercooled
water. Observations were made at constant tem­
peratures on the freezing rate of systems composed
of large_numbers of supercooled drops.
B. EXPERIMENTAL METHODS AND RESULTS
1 • .Nucleation of Supercooled Liquid Tin
In the experiments on tin, the samples were
prepared from a fine tin powder Jobtalned from
Eimer and Amend) conSisting of small spheres of
tin ranging in diameter from approximately 1 to 10
microns. (The fact that the particles were far from
uniform :in diameter complicated the interpretation
of experimental results. In future -work, it will be
desirable to perform the experiments on samples
containing drops as nearly identical as possible.)
In-the first experiments, the sample of tin powder
was mixed with a bakelite varnish -and spread as a
film on a glass slide. The slide was mounted in <:
small electric furnace built to fit on:a-Philips x-ray
diffraction apparatus. The apparatus was adjusted
to give a strong diffradion line of the crystalline
tin. The sam ole was then heated above its meltin~
point (231.89 0 C) to 2400 C. At the melting point,
the diffraction line of the solid tin disappeared.
Hydrogen gas was run through -the furnace to pre­
vent oxidation of the sample. After having been
heated above the melting point, the sam pie was
cooled and held at some temperature below its
freezing point. The rate at which the supercooled
particles crystallized was determined by measuring
the rate at which the diffraction line of selid tin
reappeared. The results of a typical experiment
are shown In Fig. 1. It was soon found that the rate
of nucleus formation was greatly increased by a
small decrease in temperature and that the tempera­
ture -control was not suffic.ien~ly sensitive to per­
mit measurements with any accuracy.
kdHCerent apparatus was :then set up In which
the -rate at which the tin particles solidified could
be measured by the rate at which their volume
changed. When liquid tin crystallizes, its volume
decreases by about five per cent. The tin powder
was first heated in air for about half an hour at
15-00 Cto give it a thin coatin~-. of oxide to separate
the -particles. It was sealed into:the 'u_lb of a dila­
tometer (see Fig. 2). The dilatomete1" was then
pumPed out and baked at a pressure of less than a
micron to :.'emove any gas. "Oct(l11 S" was then
distiiled into the dilatometer under vacuum. A
z
F
~
o
....z
~
~ lOO
2
§
TIME TO coo.. 2401; TO 130·C
TIME IN MINUTES
Ftc· I FraeUoa 01 Un cltopo rel!l&ln1nllllllro,en .. IODeU.. 0/ I1me II 1300c Irom x·raT cIala.

 nucleation. A dc!crease in temperllture of seven

degrees causes a sixtyfold increase in the nuclea­
tion rate. In observations on the rate of nucleation
of supercooled water clouds in the presence oC silver
iodide smoke, the author has observed a 'simUar
large negative temperature coefficlent{l); For a
given smoke, the rate of ice crystal formation was
apprOximately thirty times greater at .laoe than

_.
at -lOOC.
An approximate value for the activation energy
' .... of the nucleation reaction can be com~ted from
the data in' Flg. 3. The log of the reciprocal of the
time required for one third of the sample to freeze
me~ementof the rate 'ofnucleation was made by
was plotted against the reciproCal of the ,absolute
first beating the bulb to II. temperature above the temperature to give the curve in Fig. 4. This cor­
meltiDg point c[ & (265OC),and thcn. placing it in a responds to an activation energy of -2 x 105 calorie!:.
silicone oU, cOli.~tant-temperature b,aih. The 'rate The.data taken at 116.7OC has not been used because
of nucleation,wasnatermined by observing the rate nucleation at that tenlperature proceeds so rapidly
. of volume decrease as melLSlll'ed by-the motion of ~at most of the sample is frozen by the time its
the "Octoll S" along a graduated capillary tube. A ,temperature has come to equilibrium with the con­
long capUlarytube was used in the first experim(lnts, stant tempe,rature bath. .
but it-was found that appreciable error was ClUl8ed
~. Nucleation of Supercooled Water
by the ,slow dratugeof the llquid from the walls of
the time. ThiS od1ffleulty ' was m1nim1zed by uSing The author first attempted to measure the nuclea­ . !­
the oU'reservo~shown in:Fig. 2. Duiingthe melting t!on of supercooled water whUe , conduc~ , experi­
of the sample, tbe tube was held ,at an angle s6that ments at theDe-icing Research Laboratory at M.I. T.
theoUcovered~endoflbesmallfuSed quartz ~ tuhe 'Anemulsionofwaterdl-ops suspended in lub'ricating
sealed into the P11'8x capUlary. (The 'small tube W8.3 011 was c'ooled to -29OC with ' the expectation of
made offusedquartz 80Uiat it would'not melt-while measuring the nucleation rate by the rate of volume
it was being sealed in~o the pyrex cap1ll,ary). increase. This methocfwas noLSuccessfui,because
Vihen the sample had been cooled to 'almost tile de­ the solubility of water ill the oil was sufficiently
sired temperature, the tube was tipped so that the large so that diffusion rapidly took place:-from the
excess liquid ran away.fro,in the end Of the capWary ullfrozen to,the frozen dr0pH.
tube, thus for~ the ,meniscus in' a convenient
pOsl~on. Some preliminary ,studies -on water ha.ve been
~adl! in ctl:ds laboratory using -a variation-of the
T}le results' of the ' experiments, are shawn lJ,
Flg:,3. The ti~e has been plotted on a log scale to
condense the c\irves for rims made over a long,time
interval. If the chances -of a nucleus , occurrilig in 10
eacli:ttn particle were euctl, the -same and,,w ere
10
independentof'the length-of time it ,had been super­
cooled, one wo~d expect the rate of nucleation to ...z
N ' 7
decrease expone~tiallywith time. The curves;shaw
clearly that inothese exPeriments "this is not the
case. The fraction of the sample c1jstallizmg per
I
~
eo
Z 60
uniUime steadily decreaSes with ume. Some drops j
nucleate more readily t.haIl others, probably b~cause II! 40
they,are either larger tliin the others or because Z
;:
they' c'ontain certain impurities whl,ch increase the 15 30
probability of nucleus forination. The data obtained IE
as 20

~
shoUld be interpreted the behavior of super­
'cooled tin with;-wh~tever..impuritie~ , were pr(!~ent. 10
It is' probable'that tin, free of impurities, if it could
be obWned, might behave very differently.
TIME IN MIMlTE!o ,
One of :the most striking features of the data Is
th~ very great-:effect of temperature on the rate of FIC. , FucUon oll)n drop" rcnul:'IIn~ uniro.t''f .l!l: ~ luncllntl 01 IImr Irom dJlllomtftr d.a1~.

1. VOMegut, B. To be published ~' C H E MI CAL REVIEWS.

 method descr.l.bed above. In these experiments, 64
drops of distilled water weighing approximately - ­ _ _......,........._ _ _ _ _ _ -14.2·C
three milligrams each were placed in a square pat­
tern on a polished chromlum-p~ated metal plate.
On the recommendation of Dr. V. J. Schaefer of
this laboratory, the chromium surtace of the metal
.ffi!lO
~ 20
-16.O'c

o
plate was covered with a thin-film of _polystyrene by ~.,
dipping it into a solution; This-had been. found by oJ

Schaefer to lower the temperature to which the IL

010
water could be supercooled. The plate with the II:
drops on its surface was tlien placed on a thE'rmo­ ill
7
stated copper block at some temperature below ~ 6
z S
freezing. To prevent impurities in the air from
4
settling on the water drops, -the plate was covered
wHh a piece of plate glass which rested on a raised 30~~2~-4~-6~~-=~~~~~~~~~~-J
rim on the copper block. The heat transfer between TIME
the block and plate was sufficient to bring the drops
on the plate to the temperature 'of the block in less Fig. 5 rucllon.ol w:tcr drops remaining unlro:cn as a lonetlon 01 time.
than one minute. The number of unfrozen water
drops was measured as a function of time by visual
observation. Figure 5 is a curve showing the nuclea­ supercooled tin and ona supercooled cloud seeded
tion of the drops at various , t~mperatures. with silver iodide.
The data for the freezing of water drops given
Despite precautions _to keep -the water drops free in Fig. 5 can be interpreted :in terms of the rate of
from impurities, it is certaln ~tJ1-at -the drops were nucleus formation per gram of water. Figure 6
contaminated by foreign material from the atmos­
phere and from the surface , of~t~-e plate, which in­
creased the rate of nucleatio!1. -Here again the data 8r---------~----------------~
would probably be far differeI:\rfor completely pure /
I
I, water. The striking feature of -the -data 1s again
the large negative temperature coefficient which
7
I
I
I characterized the results of the - experiments on
I
a:
6

5 /
I
/
I
I

3 .0 Ie /

2.5
V"- i
~

a:

4
/
/
I

/
/ IAI
CL

i&i
3
I
/
I

I 2.0
g2
• ,/
/
1­ ~--'~ /
z
/
/
I
1.5 2
~
/
§
II
I-
~

t
1.0

0.5

0.00247
V
/
V
/

0.00250 0 .00253
-I
0

I.
.00385
-20
TEMP

-25
·c
-30 -35

~
T
Fig. 4 Nuclullon ..tt 0/ tin drops as alunctlon 01 temperat"re. Fie. e NlIeleaUDG rale at "ater drope .. a hlDcUOII til t.mp· ,Abu'e.

2. Schaefer, V. J. SCIENCE, 104, pp. 457-459 (November 15,1946).

3. Schaefer, V. J. BULLETIN- OF AMERICAN METEOROLOGICAL SOCIETY, 29, No.4,

pp. 1'75-182 (April, 1948).

r--- - - -- - - - - - - - - -- - - - --- -­
'relates the rate of nucleus formation per gram to
the reciprocal of the absolute temperatures. The
rate of nucleation was calculated from the times
required for the fir!lf 22 drops !ofreeze at the Tari­
ous temperatures. The -energy of activation com­
putedfrom the slope of the curve in Fig. 6is -1.6x1~
cal. It is interesting to extrapolate this data for
comparison with observations made by Dr. V. J.
Schaefer(2)(3) in his experiments on supercooled
clouds. If it is assumed that the liquid water con­
tent in the cloud in the cold box is of the order of
1 gm/m3, at a temperature of -25OC, according to
this data ice crystals should be appearing at the
rate of about 104 per second. Actually, with clean
air at this temperature, _no crystals are observed.
It is not until the temperature falls below -39.0
+0.1 0 C that many crystals begin to form. The rate
of nucleation in the water drops on the metal plate
is much larger than that in the water drops in a
cloud, probably because of the nucleating effect of
the surface of the plate and _chance impurities.
The sudden appearance of-large numbers of ice
crystals when the temperature is _3g 0 C or lower
indicates thafin Schaefer's experiments the increase
In nucleation rate with decreasing temperature must
be even greater than that found in this work.
C. SUMMARY
X-ray diffraction, dilatometric, and visual tech­
niques are described for measuring the extent of
crystallization of systems composed of many small
mutually Independent volumes of supercooled liquid.
Preliminary -measurements on supercooled liquid
tin and sllpercooledwater show their rate of nuclea­
tion has a vc"y large negative temperature co-effi­
cient corresponding to an activation energy of the
order of -2-x 105 calories.
ACKNOWLEDGEMENTS
The author wishes to thank Dr. D. Harker for
.his helpful advice and the use of his x-ray facilities
in thlswork, an~ Drs. I. Langmuir and V. J. Schaefer
for their Interest and many valuable suggestions.
 ·, ----- .
...,.------------:---...,....---------...,,-:::--~----------.

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