Outline

The problem: electric charge in insulators

Accidents, explosions
Basic ideas: electroneutrality, contact and tribocharging
Identity and source of charge carriers
Water with net charge
Water charging procedures
Properties of water with excess charge
Hygroelectricity
Charge exchange between the atmosphere and solid surfaces
The atmosphere as a charge reservoir




Do we understand contact charging of
insulators?
one of the earliest
manifestations of electrical
science.
Yet reproducible
experiments remain a
challenge.
A theory of charging
remains elusive.
Castle, J. Electrostatics 1997

the charging of insulators
comes from a transfer of
electrons, of ions, or of
both?
Montgomery: always
electrons
Loeb: generally electrons
Henry feels that the question
is still an open one.
I (Harper) am of the opinion...
carriers are never electrons
in an insulator.
Bailey, J. Electrostatics 2001


Electrostatic charging:
an old but still unsolved problem
it remains among the most poorly
understood areas of solid-state
physics.

Schein LB
Recent progress and continuing puzzles in electrostatics.
Science, 316, 1572-1573 (2007).

For nanotechnology:
Electrostatic force is even
larger than the inertial force,
for micromachine parts
made of insulators.
The electrification of the insulator
is not well understood, especially
at the micro-scale.
Fujisawa and Enomoto, AIST

For space research
Space suit generates 20 kV
Safety problems
Dust explosions
Fires
Pharmaceuticals

Important technologies
Polymer recycling
Electrospinning
Solid paint
Electrocopying
Consequences
The first dust explosion that was outlined in a world literature occurred in 14 December 1785 in Italy. Turin
Science Academy noticed that it was an explosion of flour dust in the centre of Turin. According to
literature all building was destroyed - reported by Rafal Porowski from HQ of SFS.
http://www.ppoz.pl/wwwold/current.htm
Charged wheat flour, sugar and polyethylene
are powerful explosives
Water and electricity
Steam electricity
Discovered in 1840 by Lord Armstrong: vapor is charged
opposite to the remaining liquid.
Electrochemical potential at V0

i
=
i
+ RT ln a
i
+ z
i
FV
Excess cations under negative potential and vice-versa.
In Earth, we are immersed in large and variable electric fields:
excess charge should be found in most places.

Sun
+
+
+
+
+
+
+
+
+
+
+
-
-
-
-
-
-
-
-
-
-
Water ion partition in interfaces
Gas bubbles and pure hydrocarbon
drops in water hold negative charge
Beattie, J. K.; Djerdjev, A. M. Angew. Chem. Int. Ed. 2004,
43, 3568.
Marinova, K. G.; Alargova, R. G.; Denkov, N. D.; Velev, O. D.;
Petsev, D. N.; Ivanov, I. B.; Borwankar, R. P. Langmuir 1996,
12, 2045.
Healy, T. W.; Fuerstenau, D. W. J. Colloid Interface Sci.
2007, 309, 181.
Kelvin dropper
http://ocw.mit.edu/ans7870/hs/physics/8.02/8.
02-s02-vl10.ram

Water and electricity
Electroneutrality of water
According to IUPAC, every pure substance is
electroneutral.
In any natural environment, we are under large electric
fields. How electroneutral are real substances?.
Amin, M. S.; Peterson, T. F.; Zahn, M. J. Electrostatics 2006, 64, 424: water
from different sources carries excess negative charge.
McCarty, L. S.; Whitesides, G. M. Angew. Chem. Int. Ed. 2008, 47, 2188: non-
electroneutrality should be considered.

Is matter electroneutral?

One of the basic assumptions of chemical
thermodynamics is that bulk matter is
electrically neutral; abandoning that
assumption allows us to contemplate, for
example, the free energy of transferring a single
ion from one phase to another.

L.S.McCarty and G.M.Whitesides, Electrostatic Charging
due to Separation of Ions at Interfaces: Contact
Electrification of Ionic Electrets,
Angew. Chemie Int. Ed. 2008, 47, 2188-2207
Can water store charge?
Ovchinnikova K, Pollack GH, Langmuir 2009, 25, 542547.
criticized by Corti HR, Colussi AJ, Langmuir 2009, 25, 65876589.
Replica, treplica.
Amin MS, Peterson TF, Zahn M, J Electrostatics 2006, 64, 424
430.
It is adsorbed of absorbed in almost any solid or liquid, where
it can impart charge:
Gouveia RF, Galembeck F, J. Am. Chem. Soc. 2009, 131, 11381.
Rezende C, Gouveia RF, da Silva MA, Galembeck F, J. Phys. Cond. Mat.
2009, 21, 263002.
Bernardes JS, Rezende CA, Galembeck F, J. Phys. Chem. C 2010, 114,
19016.
Ducati TRD, Simes LH, Galembeck F, Langmuir 2010, 26, 13763.



current geophysical research has not yet
disclosed effective models for atmospheric cloud
electrification.
Helsdon Jr., J. H.; Gattaleeradapan, S., Farley, R.
D.; Waits, C. C. J. Geophys. Res. 2002, 107, 4630.
What is the origin of atmospheric electricity?
KFM, SEPM: scanning electric potential
microscope
Kelvin method with force detection
electric
oscillation

mechanical
oscillation

mirror
laser
feedback
sample
photodetector
AC supply (1)

AC supply (2)
detector:
amplitude
& phase 2/1
DC

xyz
Kelvin force microscopy: complex and unexpected
charge distribution in every surface


A Galembeck, CAR Costa, et al., Polymer, 2001, 42, 4845; F Galembeck, CAR Costa,
et al., An. Acad. Bras. Cienc., 2001, 73, 495; FG, C Rezende, RF Gouveia, MA da Silva
Journal of Physics Condensed Matter, 21, 2009, 263002

EFM KFM
PP
Natural
rubber
Hema

PE

PP
Silica
PSAAM
/mica
Natural rubber +
sodium
polyphosphate film
Polyester
printing film
PE
Poly(styrene-butyl
acrylate-acrylic acid)
aging
alumina TiO
2
on mica
Styrene-butyl
acrylate latex
Water with net charge
Induced by electrified metal
Water dropping through a biased needle
Water dropping through a grounded needle and
passing through a biased ring
Induced by non-contacting insulator
Properties of electrified water

Experimental
Water pumped trough a needle
syringe pump
Needle is biased
or needle is grounded and water drops pass through a
biased metal ring
Water drops are collected within a Faraday cup
Charge is measured
Surface tension is determined by drop volume and
drop profile methods.

Santos, Ducati, Balestrin and Galembeck, J. Phys. Chem. C 2011, 115,
11226-11232

Water dropping from electrified needle:
experimental protocol
Seven one-minute steps
1. No water flow, no bias
(baseline)
2. Water flow, ungrounded needle
3. Water flow, grounded needle
4. Water flow, biased needle
(1 or 3 min)
5. Water flow, grounded needle
6. Water flow, ungrounded needle
7. No water flow, no bias
(baseline)



Total charge and charge increment as a function of time
0 1 2 3 4 5 6 7
-1.5x10
-6
-1.0x10
-6
-5.0x10
-7
0.0

Q
/

t

(
C
/
m
i
n
)
Time (min)
-6.0x10
-7
-4.0x10
-7
-2.0x10
-7
0.0
C
h
a
r
g
e

(
C
)
No
flow
No
bias
Water
flow
No bias
Water
flow
V=0
Water
flow
-1000 V
Water
flow
V=0
Water
flow
No bias
No
flow
No
bias
Charge/area,
charge/volume,
drop radius and
surface tension
vs. voltage
In the center of a
large Faraday cage
(3 x 3 x 4 m
3
), to
achieve low field.
within
small
Faraday
cage
Needle potential effect on water
charge
Voltage
(V)
Surface
tension
(mN/m)
0 72.790.06
200 72.710.07
-200 72.720.07
400 72.540.07
-400 72.530.06
600 72.130.08
-600 72.130.06
800 71.700.06
-800 71.680.06
1000 70.990.08
-1000 70.980.08
Surface tension measurements on water drops hanging from an
electrified needle.
Readings were recorded every 10 seconds, while the needle was
biased at different voltages.
0 200 400 600 800 1000 1200
71.0
71.5
72.0
72.5
73.0
73.5


S
u
r
f
a
c
e

t
e
n
s
i
o
n

(
m
N
/
m
)
Time (s)
Surface tension
Average surface tension at 0V
+200 -200
+400 -400
+600 -600
+1000 -1000
+800 -800
Water
dropping
from a
grounded
needle but
through a
biased ring
Positive ring bias, negative drop
and vice-versa
0 5 10 15 20 25
-1.5x10
-6
-1.0x10
-6
-5.0x10
-7
0.0
5.0x10
-7
1.0x10
-6
1.5x10
-6


Time (min)

Q
/

t

(
C
/
m
i
n
)


-2.0x10
-6
-1.5x10
-6
-1.0x10
-6
-5.0x10
-7
0.0

C
h
a
r
g
e

(
C
)

+
1
0
0

V

+
1
0
0

V

+
2
0
0

V

+
2
0
0

V

+
3
0
0

V

+
3
0
0

V

+
4
0
0

V

+
4
0
0

V

+
5
0
0

V

-
1
0
0

V

-
1
0
0

V

-
2
0
0

V

-
2
0
0

V

-
3
0
0

V

-
3
0
0

V

-
4
0
0

V

-
4
0
0

V

-
5
0
0

V

0 5 10 15 20
-3.0x10
-6
-2.5x10
-6
-2.0x10
-6
-1.5x10
-6
-1.0x10
-6
-5.0x10
-7
0.0

Time (min)
C
h
a
r
g
e

(
C
)
-600
-400
-200
0
200
400
600
f
l
o
w

1
1

d
r
o
p
s
/

m
i
n
f
l
o
w

3
0

d
r
o
p
s
/

m
i
n
f
l
o
w

3
0

d
r
o
p
s
/

m
i
n
f
l
o
w

6
6

d
r
o
p
s
/

m
i
n
n
e
g
a
t
i
v
e

d
i
s
c
h
a
r
g
e
f
l
o
w

6
6

d
r
o
p
s
/

m
i
n
f
l
o
w

3
0

d
r
o
p
s
/

m
i
n
f
l
o
w

1
1

d
r
o
p
s
/

m
i
n
f
l
o
w

3
0

d
r
o
p
s
/

m
i
n
f
l
o
w

3
0

d
r
o
p
s
/

m
i
n
V
o
l
t
a
g
e

(
V
)
0
2
4
6
8
10
Water dropping from a
grounded needle adjacent to
charged plastic sheet
Summing up
Water is electrified:
Dropping from a biased metal needle
Highly reproducible, lowered surface tension
Density and viscosity are not changed
Dropping from a grounded needle through a non-
contacting biased metal ring
Highly reproducible
Dropping from a grounded needle through a non-
contacting electret
Highly reproducible
How?
Mechanism: contacting needle
H
+

H
+
H
+

H
+

H
+

H
+

H
+

H
+

H
+

H
+

H
+

OH
-

H
+

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

2 OH
-
H
2
O + O
2

+ 2e
-

Mechanism: non-contacting ring or
charged insulator
H
+

H
+

H
+

H
+

H
+

H
+

H
+

H
+

H
+

H
+

H
+

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

OH
-

H
+
(H
2
O)
n
to the
atmosphere

i
=
i
+ RT (ln x
i
) + zFV

Problem: KFM calibration
Calibration sample:
electrodes evaporated
on Ti, over silica film on
silicon wafer

Electrodes are
polarized using an
external power supply
electrode
silica
AFM
KFM
R. F. Gouveia et al.,
J. Phys. Chem. B 2005, 109,
4631
Variable RH effect
time
Positive
electrodes
Grounded
electrodes
Biased
electrode
Grounded
electrodes
Biased
electrodes
Grounded
electrodes
Gold
electrodes
Silica
Surface silanol groups: Si-O-H and
adsorbed water
H
+
discharged on polarized
electrodes
Less mobile OH
-
and Si-O
-
groups
persist, producing domains with
excess negative charges
Grounded electrodes: vapor
adsorption followed by discharge
and desorption of OH
-
added to
surface diffusion




Model for charge build-up on silica
H
+

H
2

- - -
- - -
H
2
O
O
2

[OH(H
2
O)
n
]
-

Gouveia, R. F.; Costa, C. A. R.; Galembeck, F. J. Phys. Chem. C 2008, 112, 17193.
Electrostatic charging of hydrophilic
particles due to water adsorption
Stber silica on silicon wafer
AFM 30% RH
Kelvin Force Micrograph 30% RH
Gouveia, R. F.; Galembeck, F. J. Am. Chem. Soc. 131(32), 2009, 11381



0 100 200 300 400
-2.2
-2.1
-2.0
-1.9
-1.8
-1.7
-1.6
-1.5
-1.4
Relative humidity (RH):
30%
50%
70%
Back to
30% (obtained immediately)
30% (after 90 min)
E
l
e
c
t
r
i
c

p
o
t
e
n
t
i
a
l

(
V
)
Distance (nm)
Electrostatic pattern in silica changes with
relative humidity
Scanning the same area under different RHs: in many areas, at
high RH surface potential becomes more negative, reversible.
0 50 100 150 200 250 300 350 400
-1.50
-1.45
-1.40
-1.35
-1.30
-1.25
-1.20
-1.15
-1.10
Relative humidity (RH):
30%
50%
70%
Back to
30% (obtained immediately)
30% (after 90 min)
E
l
e
c
t
r
i
c

p
o
t
e
n
t
i
a
l

(
V
)
Distance (nm)
Another case: amorphous aluminum phosphate
Scanning the same area under different RHs: at high RH potential becomes less negative,
and back. Not reversible.

Gouveia, R. F.; Galembeck, F.
J. Am. Chem. Soc. 131(32), 2009,
11381

Large potential gradients
Steeper potential gradients in silica than in aluminum
phosphate.
0 100 200 300 400
-4
-2
0
2
4
6
Relative humidity (RH):
70%
30% (final condition)

V
/

d

(
M
V
/
m
)
Distance (nm)
Stber silica particles Aluminum phosphate particles
0 100 200 300 400
-15
-10
-5
0
5
10
15
20
Relative humidity (RH):
70%
30% (final condition)

V
/

d

(
M
V
/
m
)
Distance (nm)
The model
Ions from adsorbed water impart charge to surfaces
and absorb in bulk solids,
even in hydrophobic solids.
Ion partition is determined by chemical specific
interactions and by the local potentials.

i
=
i
+ RT (ln x) + zFV
excess [H
+
] under negative V (or [OH
-
] under V>0)
Atmosphere is a charge reservoir for insulators.
Rezende C.; Gouveia R.F.; da Silva M.A. Detection of charge distributions in insulator surfaces. Journal of Physics
Condensed Matter, 21, 2009, 263002 (invited topical review)



Analytical Chemistry 2012, DOI: 10.1021/ac3009753
Isolated metals
Charge measurements of macroscopic
samples are made using Faraday cups.
Two concentric metal cylinders
Outer cylinder is grounded
Problem: in control runs, empty Faraday cups
also build-up charge.
Hypothesis: metals within shielded environments
also acquire charge under high humidity.
CPB cylinder within a Faraday cup.
Negative charge builds up during dry-wet-dry N
2

cycles, in a shielded and grounded environment.
Copper Brass
Aluminum Chrome-plated brass
Stainless steel NiCr wire
C
h
a
r
g
e

c
h
a
n
g
e

r
a
t
e
/

1
0
-
8

C
/
s

Relative humidity/ %
Chrome-plated brass
Stainless steel
Cu, brass, silicone-coated
Al
Two metal sheets (aluminum and SS) separated by a sheet of cellulose and
enclosed within two cellulose sheets, within humid N
2
atmosphere.
Spontaneous capacitor charge
How?
Charge Partitioning at Gas-Solid Interfaces: Humidity Causes Electricity Buildup on Metals
Telma R. D. Ducati, Lus H. Simes, Fernando Galembeck
Langmuir, 2010, 26, 13763-13766. DOI: 10.1021/la102494k

Conclusion
Water with a steady charge is reproducibly obtained.
Surface but not bulk properties change.
Charge transfer is mediated by water ions: OH
-
and H
+
.
Rayleigh ratio limit can be largely exceeded under low
field and low Weber number.
Agreement with previous results and model:
Atmosphere is a charge reservoir for solids and liquids.
mediated by atmospheric water
Water adsorption and desorption, condensation and
evaporation are concurrent to ion partition.


Acknowledgements
To students and post-docs that participated
from this work (listed in the references).
To the Pronex, Millenium Institutes and INCT
National Institutes for Science and Technology
from the Brazilian and So Paulo state funding
agencies.
To Capes, CNPq and Fapesp for the
fellowships.


Can we better understand and achieve
controlled interaction with
atmospheric electricity?
cuvette wrapped
with SS screen
water
contacting SS
electrode