1

Freezing droplets
Vitalii Matyunin
Vyacheslav Chernov
Roman Doronin
Pavel Yanko
Problem 2

Place a water droplet on a plate cooled down to

around –20 °C. As it freezes, the shape of the
droplet may become cone-like with a sharp top.
Investigate this effect.
 3

First
observations
Freezing droplets 4

5 mm

T ≈ –15°C
Plan of the report 5

The shape of a freezing droplet

The shape of ice/water front

The final stage of freezing

Verification of the theory

Additional tip on the top

 6

The shape of
a freezing droplet
Freezing process (video) 7
Bond number 8

Bond number is the ratio between the gravity

force and surface tension:
3 2
a g ga
Bo  
a 
For our droplets Bo=0.3÷0.6. Therefore:
•Influence of gravity is small
•Free surface of the liquid droplet is close to
spherical
Droplet of distilled water 9
Outline shape of freezing droplet 10

The upper part of frozen droplet has a conical shape.

The surface of unfrozen water has a shape of a

sphere inscribed in this forming cone.
 11

Theoretical
model
What is the shape of ice/water front? 12

What is the shape of ice/water front?

What do we see? 13

But we don’t see the whole shape of the front.

Is it flat or concave?
Spherical recess at the top 14
Experiment 15

When the front is close to the top, we sharply pump

out the unfrozen water using a syringe
The proof by contradiction 16

Assume the shape of ice/water front to be flat.

The heat flux at the periphery is greater than in the center,
so the front moves up on its edges faster than in the center.
Simplified numerical model 17

• 2D model.
• Densities of solid and liquid phases are the same, so
the droplet does not change its spherical shape.
• The temperature of solid phase everywhere is equal to
the temperature of the plate.
• The heat flux is proportional to the length of the border
between liquid and solid cells.
Computer simulation 18
 Advanced numerical model 19

Schultz W.W., Worster M.G., Anderson D.M. (2001) “Solidifying sessile water droplets”.
 20

The final stage

of freezing
Condition of self-similarity 21

All points of the front move forward at the same velocity.

So the heat flux should be the same everywhere.
To satisfy this the front should have the shape of a sphere,
which center coincides with the vertex of the formed cone.
 Advanced numerical model 22

Schultz W.W., Worster M.G., Anderson D.M. (2001) “Solidifying sessile water droplets”.
The volume ratio 23

ice
water

Vwater : Vice = q = 0.917

 Volumes of water and ice 24

α α
90°–α 90°–α VC
V2
α r α r
V1 V1

r 3 cos 
VC ( )  
3 sin 
r 3 (1  cos ) 2 (2  cos  )
V1 ( )  
3 sin 3 
r 3 (1  sin  ) 2 (2  sin  )
V2 ( )  
3 cos 3 
 The volume ratio 25

α α
90°–α
V2
90°–α VC
α α
V1 V1

V1 ( )  V2 ( )
q
V1 ( )  VÑ ( )
Angle at the vertex of the cone 26

1,00

0,95
Volume ratio

0,90

0,85

0,80

0,75

0,70
45 50 55 60 65 70 75 80 85 90
Vertex angle (°)
 27

Verifying
the theory
Droplet of distilled water 28

65° 65°
Gathering of statistics 29

α = 63.7 ± 1.3°

q = 0.911 ± 0.006
Why q is less then 0.917 ? 30

dbub ≈ 0.1 mm

Air bubbles decrease the average density of ice!

Rising air bubbles(video) 31

Source: http://youtu.be/pyGeW_utrpY
Velocity of rising bubbles 32

Re  1 1 3

 Fbuoy  d g
Fbuoy  6
 Fdrag  3d v

2
1 gd
v 
18 

Fdrag vbub ≈ 5·10–9 m/s

Velocity of the front 33

h h 2 mm
v fr  
t 40 s

vbub ≈ 5·10–9 m/s vfr ≈ 5·10–5 m/s

 34

Additional
tip on the top
Vapor concentration around a vertex 35

High vapor flux due to

the large gradient of vapor concentration

J   D c
Distilled water 36

Low air humidity High air humidity

 37

Summary
Main results 38

• We explain theoretically and show experimentally that

during a freezing process the ice/water front has a
concave shape.
• For the final stage of a freezing process we propose a
theoretical model of self-similarity. This model predicts
that the angle at the vertex of the cone is about 65°. This
value is confirmed experimentally.
• An additional tip on the top of the frozen droplet is
formed due to an intensive deposition of water vapor.
This tip become greater when any substance is dissolved
in water.
References 39

• Sanz A., Meseguer J., Mayo L. (1987) “The influence of gravity on

the solidification of a drop,” J. Crystal Growth 82, 81–88.
• Anderson D.M., Worster M.G., Davis S.H. (1996) “The case for a
dynamic contact angle in containerless solidification”. J. Cryst.
Growth, 163, 329–338.
• Schultz W.W., Worster M.G., Anderson D.M. (2001) “Solidifying
sessile water droplets,” in Interactive dynamics of convection and
solidification, Boston: Kluwer, 209–226.
• Snoeijer J.H., Brunet P. (2012) “Pointy ice-drops: How water freezes
into a singular shape”. Am. J. Phys., 80, 764–771.
• Enriquez O.R., Marin A.G., Winkels K.G., Snoeijer J.H. (2012)
“Freezing singularities in water drops”. Phys. Fluids, 24, 091102.
• Nauenberg M. (2013) Comment on “Pointy ice-drops: How water
freezes into a singular shape” [Am. J. Phys. 80, 764–771 (2012)],
Am. J. Phys. 81, 150–151.
Novelty 40

 Condition of self-similarity

1,00

0,95

Volume ratio
0,90

0,85

 Angle prediction based on our 0,80

0,75

theoretical model 0,70

45 50 55 60 65 70 75 80 85 90
Vertex angle (°)

65°
 Very good agreement with
experimental observation
41
Experimental setup 42

Contrasting
background

Steel plate

Water solution
of KMnO4
Экспериментальная установка 43

Temperature
was measured
by thermocouples
Water solution of KMnO4 44
Water solution of NaCl 45
Center of crystallization 46

Crystallization can begin on the borders:

Droplet - air

Inside the droplet

Droplet - plate

The most intensive heat exchange is on the droplet-

plate border. Therefore, Low slope freezes instantly.
 Ice\water front 47

R
We see, that areas on the border of the droplet are
smaller, than in the center. That is why, on its edges ice-
water front moves upward faster.
Incorrect physical model 48

• Incorrect Assumption:
Horizontal ice-water front;

• Price for the simplification

Sharp pointy tip will not appear for water droplet;
Parameters of such physical model 49
Time of freezing 50
Stages of crystals formation 51

• Condensation of the vapor

• Integration of condensed liquid with the
droplet.
• Freezing of the condensed liquid. Appearance
of the ice crystals on the surface of freezing
droplet.
• Melting of the crystals.
Following cooling 52

• We observed thick (?) and short crystals.

They grew at the upper part
 Experimental setup 53

Temperature KMnO4 Vessel

Massive plate
sensors with liquid
solution
NO2
Extremely low temperatures 54

• With very low temperatures we

observed long and thick crystals – dendricity shapes.
• They still grew up at the upper part of the droplets
Boundary effect 55
What is the shape of ice/water front? 56

To predict the angle at the vertex of the cone

we need to know the shape of ice/water interface.
Spherical recesses 57
 Paradox result 58

Pointy ice-drops: How water freezes into a singular shape

Jacco H. Snoeijer
Incorrect physical model 59

• Incorrect Assumption:
Horizontal ice-water front;

• Price for the simplification

Sharp pointy tip will not appear for water droplet;
Parameters of such physical model 60

• The model consists of 3 geometrical parameters,

describing the shape of the droplet:
• Radius base R(z)
• Volume of the liquid V(z)
• Contact angle between the ice and the water

Volume of
unfrozen
liquid
Assumed flat ice-water front 61
(Hydrophob.)
Assumed flat ice-water front (Hydrophilous) 62
 Formation of the top 63

Extension
direction

• During spreading of the front, freezing volumes are

decreasing.
• The ice frame does not allow to the horizontal extension.
• The smallest top volume after freezing transfers into the
top.
Contact angle 64

Because of different contact angles

We can assume several regimes of tip’s formation
Time of freezing 65
Stages of crystals formation 66

• Condensation of the vapor

• Integration of condensed liquid with the
droplet.
• Freezing of the condensed liquid. Appearance
of the ice crystals on the surface of freezing
droplet.
• Melting of the crystals.
Assumption about extension of the water 67

• Surface tension allows to the water to expand

in perpendicular direction. Therefore, Ice-
water front spreads vertically.
68
Sault concentration 69
 Additional salts in liquid 70

Without salt With sault

We clearly see the changing of the shape of the top –

from thin and sharp to thick and
short, almost cylindrical.
Thick Tops 71

NаСl concentration, %
Salt concentration, gr\l 72

0,25 4

0,5 8

1 16

2 32
Freezing process 73