3rd International Webinar on Material Science & Nanotechnology

Study of surface properties

of molten Tin, exposed to air
up to 600 K
Dimitar Lyutov, Plamen V. Petkov, Nasko Goriunski,
Boyan Todorov and Hristo Iliev

16 – 17 SEPTEMBER 2021, ONLINE EVENT

 Outline of the presentation
• Surface tension definition
• Applied method and aim of the study methods
• Experimental setup, procedure and samples
• Theoretical analysis summary
• Measurement of the surface tension evolution
• Analysis of surface tension
• Discussion of the obtained results
• Summary

2 September 5, 2021
 Surface tension is measured as the energy required
Surface Tension to increase the surface area of a liquid by a unit of
area. The surface tension of a liquid results from an
Definition imbalance of intermolecular attractive forces,
the cohesive forces between molecules

Important factors qualifying solders energy

𝑊
➢Low melting temperature σ=
Δ𝑆
➢Low surface tension
surface area
➢Wetting
Appropriate surface tension ranges within 400-700 mN/m
Lower surface tension facilitates the soldering process and improves the
solderability

Exposure to air may cause reaction with oxygen and formation of dielectric oxides

3 September 5, 2021
Applied method and the aim of study 1000

x 1000
100 How the accumulation of oxides on the liquid
10
Sn  98% solder surface influence the surface tension?
Pb  2% • Is the surface tension of molten solder can be

Counts, x103
1 reliably measured
0.1 • What is the law of surface tension evolution

0.01 Bruker AXS Handheld

Inc. S1PXRF Spectrum
0.001
0 5000 10000 15000 20000 Wilhelmy plate suitable because:
Energy, kEv
• provides sufficient surface area to contact the
Wilhelmy plate method liquid solder.
• sufficiently sensitive to surface tension
P = 2.d + 2.L changes because of oxides accumulation at
𝐹 the surface
𝜎=
𝑃. 𝑐𝑜𝑠 𝜃
Measurement performed
after cooling the sample

4 September 5, 2021
Experimental setup pulley

• General conception:
measurement of
weight during motion
of z-axis table
• Zero contact angle non-
between the plate expanding
and the melt Wilhelmy plate string
with thermally
isolating holder
setup including the controllers
Glass isolating
and the computer. weight
container
oven
Z-axis
balance
movable
scale
table
support of the system

5 September 5, 2021
 12

Pb

Procedure and samples:

11

10
Density, g/cm3

8
Solder Melt. Temp., K Pb, %
Sn+2%Pb
7
Sn Sn 100 505(232C) 2
6
200 220 240 260 280 300 320 340 360
350
Temperature, Centigrades

300
y = 0.37x + 88.45
R² = 0.98

Temperature OC
250
226.3± 2.3 C
𝑡𝑖𝑛 200 Melting Solidification
Molten Sn at Beginning of Usually after y = -0.28x + 888.70 Cooling
the desired ∆𝑡𝑒𝑥𝑡 measurement 1200 s 150 R² = 0.99

temperature Heating
100
y = 0.59x + 54.92 y = -0.13x + 562.21
R² = 0.99 R² = 0.98
50
0 1000 2000 3000 4000
Time, s
Typical heat up and cool down diagram
Beginning of time
recording
6 September 5, 2021
 Measurement procedure
700
Second and third
• The measurement procedure starts with measurement performed 339.00.6 C
650
temperature stabilization of the sample after each surface

Surface tension, mN/m

cleaning
• Before each measurement, the surface is 600

carefully cleaned by removal only of topmost

550
oxide layer Temperature
500 reduced to 320C Accumulation
• At the given temperature at least three of surface oxide
consecutive measurements are performed layer
450

• Usually, the reproducibility takes place for the last 400

two measurements 0 200 400 600 800 1000 1200
Time, s
The measurement New measurement
performed after the after 1200 s with
first surface cleaning dipped Wilhelmy
plate
7 September 5, 2021
 Measurement of the surface tension evolution
700 700

650 (2) (2), (3): Second and third 650 289.9±0.6C

measurement with

Surface tension, mN/m

Surface tension, mN/m

(3)
600 reduced surface 600 (2)
246.2±0.6C concentration of Pb (3)
550 550

500 First measurement 500

with abundance of Pb
450 on the surface 450 First measurement with
abundance of Pb on the surface
400 400
0 200 400 600 800 1000 1200
0 200 400 600
Time, s
800 1000 1200
Reproducibility of the 700 Time, s
700
second and third 311.7±0.6 C

650 278.9±1.1C measurements is higher 650

(2)

Surface tension, mN/m

for ≤ 270C than for the
Surface tension, mN/m

600 (2) case ≥ 270C

600
(3)
550
550
500
500
First measurement
450 First measurement with
450 with abundance of Pb
abundance of Pb on the surface
on the surface 400
400 0 200 400 600 800 1000 1200
8 September 5, 2021 Time, s
0 200 400 600 800 1000 1200
Time, s
Theoretical analysis summary
Cleaned the surface of liquid
Theoretical study goal: Finding a suitable relation describing
solder: removal of the top
liquid metal surface oxidation process over time
surface layer, tin = 0 s

Collected sample of measured Applied the transformation for Extrapolation to initial

surface tension: 400-500 s since beginning of surface tension after the
Si  S(t) the surface oxidation cleaning of the surface:
at desired constant temperature 𝑦𝑖 = 𝑓exp
𝑆𝑖
𝑦𝑖𝑛 =a ∆𝑡𝑒𝑥𝑡 +b
for time: 𝑡 = 𝑡𝑖𝑛 − ∆𝑡𝑒𝑥𝑡 𝑔

Estimation of the initial

surface tension at the clean Obtained linear relation:
surface 𝑦=a 𝑡+b
𝑦𝑖𝑛
𝑆𝑖𝑛 = g ln 𝑓

9 September 5, 2021
Example of surface tension evaluation at 339.0 C
20 14 850
Hundreds

Standard deviation, in surface tension, mN/m

18 f = 1106 Wilhelmy plate
Linearized surface tension 103

y = 5.77x + 653.28 12 800

16 g =-80 R² = 0.98
confirmed

Surface tension, mN/m

14 10 tangential 750
Case 2 length
12
8 700
10
8 y = 3.74x + 470.54 6 650
Case 1 R² = 0.99
6 4 600
4 y = 1.38x + 433.98
Case 3 Standard
628.9±4.3 mN/m R² = 0.96 2 deviation 550
2
Surface tension
0 0 500
0 50 100 150 200 0.007 0.008 0.009 0.01 0.011 0.012 0.013
𝑡 = 𝑡𝑖𝑛 − ∆𝑡𝑒𝑥𝑡 Wilhelmy plate length, m
Time, s
From literature available data was
Parametrical study to confirm that the correct
found: 554.7±27.2 mN/m or 13.3%
tangential length of measuring plate is
selected in calculations:
𝑆𝑖
Linearized surface tension is 𝑓exp 𝑔
Reason: high sensitivity of the calculated
Where Si is the measured surface tension Si  S(t) surface tension from Wilhelmy plate
tangential length
10 September 5, 2021
 Discussion of the obtained results 70
6
704.1± 12.2 mN/m
60
5
T=246.2±0.6Cy = 0.01x + 1.27

Linerarized surface tension

Linearized surface tension

R² = 0.99 Regardless of the surface 50

y = 0.12x + 12.44
R² = 0.99
4
y = 0.005x + 1.391 kinetics, a linear relation is 636.0±17.4 mN/m
40
3
R² = 0.963
obtained for the first 400 s: T=289.9±0.6C
30 y = 0.02x + 15.70
𝑦=a 𝑡+b R² = 0.98
2
y = 0.004x + 1.409
R² = 0.994
The proposed transformation is 20
1 confirmed 10
y = 0.02x + 11.98
R² = 0.93

0 0
0 100 200 300 400 0 100 200 300 400
Time, s • Above 290C the oxidizing Time, s
30
process proceeds with 20
y = 0.05x + 8.20 18
25 R² = 0.99 higher speed with 636.8±19.4 mN/m
Linearized surface tension

16

Linearized surface tension

possible formation of 14 T=311.7±0.6C
20
Sn2O3 12
y = 0.04x + 3.17
R² = 0.99

15
y = 0.03x + 9.28 • leads to obvious 10
R² = 0.99
differences in the initially 8
10
measured surface 6
y = 0.006x + 3.074
R² = 0.919
5 664.4± 20.4 mN/m tension compered to < 4
T=278.9±1.1C 270C with possible 2 y = 0.004x + 2.209
0 11 September 5, 2021 R² = 0.9756

0 100 200 300 400 500 formation of SnO 0

Time, s 0 100 200 300 400
Time, s
Estimation of surface
tension at the beginning of Melting point Sn + SnO Sn + SnO + Sn3O4

measurement 750

Sn + Sn2O3
700
• The liquid surface exposed to air begins

Surface tension, mN/m

Level of
immediate oxidation after topmost layer surface
650

cleaning covering
600
with oxides
• At the beginning of the measurement the 550

surface is already partially populated with

500
oxides that cause increase of the surface 200 250 300 350 400
Temperature, C
tension comparing to the pure liquid
Estimated surface tension based on data in
Yuan et al. J. Colloid Interface Sci 254, 338–345
(2002)
12 September 5, 2021
 Discussion of issues and problems
• Temperature stability and temperature gradient on liquid/gas
interface
• Cleaning of measuring plate. Very often oxides are
accumulated in the Ni based Wilhelmy plate and distort the
measurements
• Sometimes the dipping occurs angles slightly different from
normal direction
• Solder dewetting from the Ni plate can take place occasionally

13 September 5, 2021
 Summary
• The developed basic equipment allows to be investigated the surface
oxidation kinetics of liquid tin

• The surface tension evolution during the formation oxide phase on the
surface can be transformed to a line and this way by the recording of
initial time, can be predicted initial surface population by oxides.

• If perfectly clean from oxide surface is obtained then the liquid tin
surface tension can be evaluated.

• Future investigation will include analysis of surface tension in different

atnospheres.

14 September 5, 2021
15 September 5, 2021