Measuring

Measuring interfacial
interfacial properties
properties using
using
Electroacoustics.
Electroacoustics.

Andrei Dukhin

Dispersion Technology Inc.

Bedford Hills, NY 10507, USA

What is Electroacoustics?
It is Electrokinetics at high frequency.
Why frequency being high is so important and different?
Liquid becomes compressible and supports sound waves.
What is Electrokinetics?
It is phenomena associated with electric charge separation at interfaces
structure known as Electric Double Layer.
Why electric charges separate at interfaces?.
- adsorption of ionic species;
- dissociation of the surface chemical groups;
- liquid structuring near the surface causing variation in ions solubility;
Why is it called Double Layer?
This structure consists of the surface charge layer that is
bound to the one phase and screening diffuse layer of
counter-ions located in the liquid phase.

Stern layer

Negatively charged
Diffuse layer

Positively
charged
particle

Debye length -1
Stern plane

Slipping plane

Why do we need to know -potential and Debye length?

1. Double layers protect particles against aggregation when they collide
undergoing Brownian motion. Intensity of electrostatic repulsion depends
on -potential. Stability threshold is about 25 mV;
2. Characterizing adsorption of surfactants, even non-ionic;
3. Characterizing properties of macromolecules, proteins;
4. Micro-fluidic devices;
5. Controlling particulates adhesion, coatings;
6. Quality control, reproducibility of products.

Are there any other methods besides Electroacoustics for measuring -potential ?

Particulates.
Electrophoresis motion of particles under influence of electric field.
Speed of motion depends on -potential. There are two versions
depending on method of monitoring particle motion Electrophoretic
Light Scattering and Micro-electrophoretic Image Analysis.

Porous bodies.
Streaming Current/Potential electric signal generated by liquid moving
through a porous body under influence of the pressure gradient.
Why do we need Electroacoustics if these other methods exist?
Electrophoresis is not suitable for characterizing concentrated systems.
It requires dilution that could affect -potential.
Electrophoresis has problems at high ionic strength, above 0.1 M due to
high conductivity and related heat production.
There is no method that would work for both, particulates and porous
bodies.

Zeta potential probe.

1. Means for generating relative phase motion: particles relative to the liquid,
or liquid relative to the matrix of porous body.
2. Means for monitoring generated signal.
3. Software based on appropriate theory for calculating -potemtial
from generated signal.

0.8

P(t)

U(t)

dU/dt

M*dU/dt

0.6

Electroacoustic
Zeta
0.4 Probe
Ultrasound pressure P(t)
0.2
0.0
-0.2
-0.4
-0.6

U p m

p m
~ P
m

Ultrasound generates motion of particles relative to the liquid when their densities
are different.
0.8
0.6

- -

- -

Electroacoustic
Zeta
0.4 Probe
0.2
0.0

-0.2
-0.4

m
~ P p
m
-0.6

- +
-+ +
-+
- - ++
+

15
1. Piezo-crystal
generates ultrasound pulse that
C V I O utput
eventually reaches dispersion through the gold
17
electrode.

2
RF pulse in put
23

23

Figure 6

1
13

2. This Ultrasound generates motion of particles

relative to the liquid when their densities are
different.

13

6
5

4
3
off-th e-sh elf
piezoelectric
tran sducer

16
Stainless steel
sh ell

3. This motion generates dipole moments for

particles.

Q uartz
D elay
R od

10
C eram ic spacer

61

4. These dipole moments generate oscillating

electric
potential on GOLD electrode only.
18

9
Buffer
R od

11
21
22
12

14

5. Stainless steel shell is outside of sound field

with electric potential = 0.

19
20

6. Difference in electric potentials between

Stainless steel shell and Gold electrode creates
14
electric current : Colloid Vibration Current
16
10

Figure 6A

p m

A
P
m
4

DT Colloidal Silica LUDOX TM for Calibration and Demonstration

Mean Value

Lot variation

DT Precision

mean particle size [nm]

31

-potential [mV]

-38

0.5

pH

9.3

+0.1, -0.4

0.01

conductivity [S/m]

0.170

0.05

0.005

particles density [g/cm3]

2.2

0.01

weight fraction, %

10

Parameter

0 2

pH

9 0.9
0.8

-10

zeta [mV]

zeta
0.6
-20
0.5
0.4

-30
conductivity

-40

0.3
0.2

conductivity [S/m]

0.7

Colloid Vibration Current and corresponding -potential for silica CMP 200
continuous measurements.
18
16
50%wt

12
10
8
6

10%wt

4
0

2
0

-10

zeta [mV]

-20
-30
-40
-50

100

200

300

400

500
600
time [minutes]

800

900

1000

Precision of the potential characterization is about 0.2 mV.

Minimum sample volume is 1 ml control.
Measurement time 15 sec 2 minutes, depending on solvent.
10%wt

-60
-70

700

50%wt

1100

CVI*10E-6

14

pH titration of rutile 7%vl and alumina 4%vl

50
40

zeta potential [mV]

30

alumina

20
10

IEP

IEP

0
2

-10
-20
-30
-40
-50

rutile

7
pH

10

11

12

Zeta potential of alumina AKP-30 at 3%vl

versus KCl concentration
70
0.01 M
60

zeta [mV]

50

40

30

20

88mV
mV
10

0
0.0

0.2

0.4

0.6

0.8
1.0
1.2
KCl concentration in M/l

1.4

1.6

1.8

2.0

Titration of 40%wt kaolin slurry with hexametaphospate at different starting pH

Optimum Hexametaphosphate
concentration is 0.6 % relative
to the weight of kaolin.
initial pH

-12

6.5
8.8
9.5
10.5

-16

zeta [mV]

-20

It is important to maintain high pH, around pH=10.

-24
-28
-32
-36
0.0

0.2

0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
hexametaphosphate to kaolin ratio by weight in %

2.0

2.2

0.8

porous
body

0.6

Electroacoustic
Zeta Probe
0.4
Ultrasound pressure
0.2
0.0
-0.2
-0.4
-0.6

250 microns

Monitoring presence of sedimenting large particles / aggregates in

opaque dispersions. Precision 0.1% of the solid content.
Ludox only
Ludox + 0.1% Geltech
Ludox + 0.3% Geltech
Ludox + 0.5% Geltech
Ludox + 1 % Geltech

5.4E+06
5.2E+06

CVI magnitude [mV*(sec/g)^1/2]

5.0E+06
4.8E+06
4.6E+06
4.4E+06
4.2E+06
4.0E+06
3.8E+06
3.6E+06
3.4E+06
0

50

100
150
time [minutes]

200

250

Seismo-electric current : Streaming current in non-isochoric mode.

1.Frenkel J. On the Theory of Seismic and Seismoelectric
Phenomena in a Moist Soil, 1944
2.re-published, J. Engineering Mechanics, 131, 9, pp. 879-887 (2005).
Overlapped DLs

I see

RT m m sinh

D (~ r 2 )e P
F s
2

Isolated DLs

Isee

0m Ks
[
Km

1
m ]P
E E E Msc

e (1v )[ ]
1 s
Mm Mp
Mp

Porous chromatographic silica, 4 samples with the same porosity and

different pore size Quantahrome Corp.
Overlapped DLs

relative value of seismoelectric current

8
7

ethanol

6
5
4
3

Isolated DLs

distilled water

2
0.1 M KCl water solution

1
0
30

40

50

60

70

pore diameter [nanometer]

80

90

100

CONCLUSIONS
Electroacoustic Zeta potential probe can perform functions of:
1.

Electrophoretic instruments (ELS and Image)

2.

Streaming Current for porous bodies

3.

Sedimentation analysis

4.

Turbidity analysis of aggregative stability

5.

Porosimetry ????

6.

Particle sizing ????

COMBINED in one instrument !!!

Measurement size of ions (nm) combination of Acoustic and

Electroacoustic 50-60 years ago Bokris, Yeager, Zana.