ECS Transactions, 11 (20) 71-81 (2008)

10.1149/1.2912050 © The Electrochemical Society

Electrochemical Deposition in RF-irradiated Solutions – A manifestation of

Induced Long Range Order?

Y. Katsir1,2,*, L. Miller 3,*, Y. Scolnik2, Y. Aharonov 2, E. Ben-Jacob 2,#

(1)
Department of Chemistry Bar Ilan University, Ramat Gan 52900, Israel
(2)
Department of Physics and Astronomy, Tel Aviv University, Tel Aviv 69978, Israel
(3)
Department of Materials Engineering, Technion, Haifa 32000, Israel

Electrochemical deposition (ECD) in radio frequency (RF)-irradiated ZnSO4

solutions is similar to that in solutions prepared from nanoparticles doped
(NPD) water and both are very different from that in control (RO water)
solutions. It was found that RF and doping treatments have dramatic effects
on the deposition morphologies from microns to centimeters. Here we
examine the idea that the observations resulted from long range order induced
by the treatments. We reason that the long range order is mediated by the
formation of network of nanobubbles (and nanoparticles for the NPD water)
with a non random organization, and propose that the network is the outcome
of bubble-bubble exchange interactions, resulted from water order around the
bubbles. To further test the idea of induced long range order we present
preliminary results of Isothermal Titration Calorimetry (ITC) experiments of
mixing of NPD solutions with control solutions, and of optical activity of the
NPD water.

(*) These authors have equal contribution.

(#) Corresponding author: Email eshel@tamar.tau.ac.il;

Introduction

During the past two decades, much effort has been devoted to study the effects of radio
frequency (RF) treatment of water (1-18). The following effects of RF-treatment were reported:
1. The formation of gas nanobubbles (2,3,10,13). 2. A decrease in surface tension from 72 to 68
dyn/cm (9). 3. An increase of 30% in the infra-red (IR) bands (3200 cm-1 - strong hydrogen
bonds, 3400 cm-1 - distorted hydrogen bonds and 3600 or 3750 cm-1 - non bonded molecules
(10). 4. An increase in the concentration of atomic hydrogen (9). 5. Modifications in the spectra
of dissolved hydrophobic fluorescent molecules (but not the spectra of hydrophilic ones) (11). 6.
Changes in the zeta potentials of test particles immersed in RF treated suspensions (6,7). 7. An
increase in growth rate of bacteria grown in RF treated aqueous solutions (19, 1). 8. Changes in
the morphology structures of depositions formed by ECD in RF-treated solutions (19).

More recently, detailed studies of the effects of RF-irradiation (in the MHZ frequency range)
and of nanoparticles doping on ECD in thin circular cells were performed (20) and focused on
comparison between the deposition structures of growth in treated and in non treated solutions.
Using scanning electron microscopy (SEM), it was found (20) that in addition to the changes
reported in (19), the RF-treatment effects span on all scales, from the microscopic structure
through the micron-scale organization to the macroscopic pattern.

Following references (1, 20), we reflect on the assumption that the effects are mainly
mediated via the formation of stable network of nanobubbles in the treated solution. Since the

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above phenomena can last for hours after treatment, they point that the RF-treatments of water
and aqueous solutions induce some long lived (hours) physical alterations in the water (dubbed
“water memory”). Additional observations that RF-treatment does not have an effect on de-
gassed water and out-gassing of RF-treated water and solutions erases all the effects, led to the
idea that the formations of gas bubbles play a key role (10).

Still, the idea of endured (for hours) nanobubbles is largely discarded for the following
reasons: 1. Nanobubbles are expected to dissolve rapidly due to the high Laplace pressure (the
internal pressure due to the interfacial radius of curvature). 2. These effects contradict the current
commonly accepted theories of water (21-28). 3. Long lived effects are in contradiction with
thermodynamics (assuming that the water and solutions have to be close to equilibrium) since the
typical relaxation times in water are very fast.

Here we follow the new paradigm presented in (20), which is based on the notion of
collective (mutual) stabilization due to bubble-bubble exchange interactions (assumed to be
mediated by the water order that is induced in the vicinity of each bubble by its shell of ordered
water molecules). It is further assumed that the exchange interactions cause the nanobubbles to
organize into a pliable network with hierarchical organization (clusters of small bubbles around
larger ones and clusters of clusters). The networks induce long range structural and orientational
order in the water, and consequently elevated stability that explains long decay time of the RF-
treatment effects. More specifically, the idea is that due to bubble-bubble interactions, the
smaller bubbles surrounding the larger ones (that serve the hubs of the clusters or keynote
bubbles) and hold them against the Archimedes force. The idea was tested in (20) by showing
that ECD in solution made from NPD water is similar to that in RF treated solution but endures
for months. It was suggested that in the NPD water the nanoparticles presumably replace the
large gas nanobubbles as the hubs of the network. Since unlike the large gas nanobubbles, the
nanoparticles can not expand and float, they provide stable anchors to the entire network of
nanobubbles affording it which has built-in stability.

We note that the gas-water interface of the nanobubbles is hydrophobic and therefore at the
interface the water molecules form clathrate shells with an “ice-like” structure. This assumption
is supported almost directly by measured changes in IR spectroscopy (10).The ordered shells
induce order in the water molecules surrounding the nanobubbles that can extend up to a micron
in range. This idea is indirectly supported, for example, by the effect on zeta potential (11) and
the fluorescence of hydrophobic molecules (6,7). We emphasize that this picture also provides a
putative explanation to the unexpected effect of the nanoparticles doping – the dramatic
stabilization of the RF-treatment anomalous effects.

Clearly, many additional experiments as well as theoretical investigations need to be

performed in order to validate and substantiate the new idea. Here we present very preliminary
results of experiments that were devised to test water properties that can be associated with the
existence of induced long range order - polarimetry measurements of the optical activity (in
terms of circularly and elliptically polarized light) of the NPD solutions using the Circular
Dichroism (CD) method and relative free energy measurements using Isothermal Titration
Calorimetry (ITC). The CD measurements seem to indicate that the NPD solutions have optical
activity (spontaneous left-right broken symmetry). The ITC measurements (of injecting NPD
solutions into control ones and vice versa) indicate that the NPD-water solutions have lower free
energy. Both results are consistent with the idea of induced long range order.

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Electrochemical Deposition (ECD) of the treated solutions

The ECD experimental procedure

The experiments reviewed here were performed in quasi 2-dimentional electrochemical cells
with a circular geometry. The electrolyte (Zinc Sulphate) solution is held between two Perspex
plates with 0.3mm spacing. The ECD cell consists of a central copper plate cathode with a
diameter of 30mm and a thickness of 0.3mm, and a circumferential copper wire (0.5mm
diameter) anode that forms a circle with a diameter of 93.5mm. Zinc Sulphate solutions are
usually prepared from reverse osmotic (RO) water and using commercial Zinc Sulphate
(ZnSO4*7H2O, Sigma-Aldrich). The ECD process was performed under constant voltage
conditions while monitoring the response current.

For the electron microscopy characterization the cells were cooled at the end of the deposition
(while the applied voltage is on) using liquid nitrogen for fast freezing and then the depositions
were dried in a vacuum desiccator and kept until they were inserted into the microscope chamber
(ultra high vacuum). The solutions conductivity was monitored before deposition and found to be
18.9x10-3 siemens with ± 0.15x10-3 siemens variations for all cases.

For the RF-treatment electromagnetic signals with a narrow band located at frequency of 915
MHz was used and broadcasted through a linear antenna that is immersed in water tank at 25 °C.
50 ml of zinc sulphate solution were irradiated in a glass bottle that was placed adjacent to the
antenna in the same water tank.

The NPD solutions are Zinc Sulphate solutions prepared from NPD water - water that is
doped with nanoparticles (Barium titanate BaTiO3) under RF-irradiation - NeowaterTM provided
by Do-Coop Technologies Ltd. The process starts with reverse osmosis (RO) water that is kept
below the anomaly point (i.e. below 4°C) and is irradiated by RF signal at 915 MHz at a power
of 60 watt. After 10 minutes of RF-irradiation, sub-micron size powder of barium titanate that is
heated to 900°C is dropped from the furnace into the water and the RF- irradiation continuous
for additional 5 minutes. Then the water is placed at room temperature for two days, until most
of the source powder (that contains larger particles) sinks to the bottom and the clear part of the
water is separated. After the doping process most of the particles have almost perfect spherical
shape, their diameter ranges between 10-100 nm and it is estimated that there are less than 1012
particles per 1ml (for more details see (20)).

The effect of RF and NPD treatments on ECD

We present a comparison of the microscopic structures of the depositions during growth in

control solutions (C), RF-treated solutions (RF) and solutions made from NPD-water (NPD) at
different magnifications using SEM. We note that three classes of growth conditions were
selected; 1. Low voltages, such that the ECD process for (C), (RF) and (NPD) yield dense-
branching morphologies (DBM) on the macroscopic scale. 2. High voltages such that dendritic
morphologies are observed on the macro-level for the three types of solutions. 3. Intermediate
voltage (V=12.4V) such that for (C) dendrites are observed on the macro-level and the DBM is
exhibited for (RF) and (NPD). Figure 1 presents a comparison between the micron scales
ordering of the DBM deposits. The results depicted in these micrographs illustrate significant
differences between the micro-scale structures of the depositions developed in the control

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solutions vs. those developed in the RF-treated solutions and in the solutions made from the
NPD-water.

Figure 1: Secondary electron (SE) SEM micrographs of DBM growth on the micro-level
for V=8.0V and C=0.1M for (C) – pictures (a) and (c), (NPD) – picture (b) and (RF) –
picture (d).

The results show that for these growth parameters the DBM deposition in the control
solutions is mainly composed of very wide dendrites while the depositions for both (NPD) and
(RF) are composed of narrow branches. The white bulges at the ends of the branches and the
dendritic tips are the results of equilibration and oxidation. The patterns shown in these pictures
provide a clear illustration that the effects of the RF-treatment and nanoparticles doping are
similar and that are both act as singular perturbation. We note that few non dendritic branches
can also be observed in the case of control solutions as can be seen in (c).

Figure 2 presents a comparison between the dendrites developed at high voltage (V=13.0V)
for (C), (NPD) and (RF). The singular effects of the RF-treatment and the nanoparticles doping
are reflected in the dramatic changes in the electron microscopy observations. We also show that
depositions grown in an RF-treated solution have similar structure to that of depositions grown in
control solutions two hours after the treatment. These observations demonstrate that the effect of

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the RF-treatment does not result from irreversible modifications in the chemical composition of
the solutions. Thus, the results support our proposed picture that the effects are mediated via
physical changes in the water structure induced by the nanobubbles.

Figure 2: SE SEM micrographs of dendritic growth V=13.0V and C=0.3M for (NPD) –
picture (a), (C) – picture (b), (RF) – picture (c) and (RF after two hours) – picture (d).

The results show the similarity in the microscopic structure between the depositions grown in
the RF-treated solution and depositions grown in solution made from the NPD-water. Both show
the existence of additional long-range order in comparison to the depositions grown in the
control solutions. We emphasize that the depositions in (b) and (d) are composed of small
dendrites (smaller tip curvature) and more ordered side branches than the ones for (RF) and
(NPD). These small dendrites are distorted in the pictures here because of the smaller tips are
subject to faster equilibration during the preparations for the electron microscopy samples.
Comparing pictures (a) and (c) we noticed that the effect of the NPD-water is stronger than that
of the RF-treatment in the sense that there is more pronounced ordering. Comparing pictures (c)
and (d) we note that after long time (hours) the effect of the RF-treatment fades away as reflected
by the fact that the deposition becomes similar to that grown in the non treated solution. These
observations suggest that the effect of the RF-treatment is connected with reversible physical

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changes – the formation of long range order, and not with irreversible chemical modifications of
the RF-treated solutions.

Optical activity of the NPD solutions

In this section we present very preliminary results of polarimetry measurements on the NPD
water that were devised to test signatures of induced long range order. The optical activity (in
terms of circularly and elliptically polarized light) of the NPD solutions was measured using the
Circular Dichroism (CD) method.

The Circular Dichroism (CD) experimental procedure

The CD spectroscopy aimed to detect absorption differences between left-handed and right-
handed (L and R) polarized lights passed through aqueous solutions. Such differences can be
generated from optically active (chiral) molecules immersed in water, distribution of molecules
or nanoparticles or any other induced ordered structures in the water or solutions. The CD
spectroscopy is widely used to investigate proteins properties such as folded/open structure,
secondary and tertiary structures (29). Commonly the temperature of the measured solution can
be varied thus enabling to detect the kinetic of structure changes such as thermal unfolding of
proteins (30). The CD is also used to clarify conformation of DNA in liquid/solid interface (31),
determined self-assembles of polymeric nanoparticles (32) and investigate molecular chirality in
general (33).
The measurements reported here were performed using a Jasco K851 CD polarimeter at room
temperature (298K). The spectrum was scanned between 190nm and 280nm using 1nm and 10
seconds increments. In order to increase sensitivity and resolution we ensured very long optical
pathway by using 10cm quartz cuvette (compared to 1mm or smaller in regular mode of
operation).

Circularly polarized light of NPD solutions

The results indicate that the NPD water shows circular dichroism. Two typical CD spectra
performed in different batches of NPD water, relative to the CD spectra of DDW (that was used
as the baseline), are shown in Figure 3. We note tat the detected magnitude of the optical activity
of about 0.5 millidegree is similar to the effect of 10-5-10-6 mole of ordinary peptide solution.
Hence it is not a negligible level. CD measured differences in the absorption of left-handed
polarized light versus right-handed polarized light arise due to structural asymmetry - The
absence of regular structure results in vanishing CD intensity, while an ordered structure results
in a spectrum which can contain positive and/or negative signals. Therefore, we propose that the
existence of non vanishing signal in the CD spectra of the NPD solutions might be associated
with the formation of long range orientational order in the NPD water, formed by the network of
nanoparticles and nanobubbles. Clearly, these are just preliminary results and many more
observations need to be performed to reach a firm conclusion

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Optical Activity of NPD water

1.5
1.3

circularly polarized light (mdegree)

1.1
0.9
0.7
0.5
0.3
0.1
-0.1
195 205 215 225 235 245 255 265 275
-0.3
Wavelenght (nm)
-0.5
-0.7
-0.9

Figure 3: Optical activity of NPD water relative to DDW spectrum. The red and blue
curves are measurements different NPD water batches, measured at different dates.

Free energy of NPD treatments

In this section we present preliminary results of Isothermal Titration Calorimetric (ITC)

experiments aimed to check if NPD treatment can induce changes in free energy. The idea is that
the formation of networks of nanobubbles and nanoparticles with non arbitrary organization and
the formation of long range order should lead to a decrease in the free energy.

ITC experimental procedure

In ITC, a syringe containing a "ligand" solution is titrated (µl by setting) into a cell containing
a solution of the "macromolecule" (1.4 ml) at constant temperature. When ligand is injected into
the cell, the two materials interact, and heat is released or absorbed in direct proportion to the
amount of binding. It is important to emphasize that in exothermic reaction (increase in the
temperature of the sample cell), the reference cell is heated. Hence, in this case the sample cell is
kept isolated and the relevant thermodynamic potential is the Enthalpy while in the opposite
situation of endothermic process, the sample cell is heated and hence the relevant
thermodynamic potential is the Gibbs free energy. This introduces an inherent asymmetry
between endothermic and exothermic processes that can play important role in the interpretations
of the measurements.

We also emphasize that the ITC method was originally devised and is usually used as a
thermodynamic technique for monitoring chemical reaction initiated by the addition of a binding
component in small droplets that are injected into a solution with the target agents. It has become
the preferred method for characterizing the energy of chemical reactions (34-36) and of bio-
molecular interactions. The method is also applied to measure hydrophobic interactions (37) and
the entropy of mixing of solutions of weakly or non-interacting (chemically) molecules and/or
nanoparticles (36, 38, 39). In the latter cases (for example when solutions with L and R
enantiomers are mixed (40), the changes in free energy are very small and one can doubt the
validity of the measurements in such cases.

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In the experiments reported here, we performed sets of 4 different injections by using two
types of 0.02M Zinc Sulphate solutions - RO solution made from RO water and NPD solution
made from NPD water. The 4 types of injections are (a) RO into RO, (b) NPD into RO, (c) NPD
into NPD and (d) RO into NPD. We have used the no stirring mode (to avoid possible
interference with the assumed long range order in the NPD water. The measurements were
performed at a cell temperature of 30°C. We tested the effects for different injected droplet sizes
and found that 50ȝl droplets gave the best results. We adjusted the time between injections to be
longer than the observed relaxation times and adjusted the injection time according to the
droplets volume.

Free energy of mixing of NPD solution and RO solution

Representative results are shown in Figures 4 and 5. To make the comparison more
transparent we show in Figure 4 the results relative to the RO into RO injections and in Figure 5
relative to NPD into NPD. For each case we show two out of several injections to demonstrate
the level of reproducibility. The results indicate endothermic reaction.

Figure 4: ITC measurements of injection of NPD into RO (Black curve – the endothermic
curve), RO into NPD and NPD into NPD ((Red and Green curves that are close together)
relative to the injections of RO into RO.

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Figure 5: ITC measurements of injection of NPD into RO (Red curve – the higher
endothermic curve), RO into RO (Black curve – the lower endothermic curve) and RO
into NPD (Green curve – the almost horizontal curve) relative to the injections of NPD
into NPD

Inspection of these results indicates that the RO into NPD and NPD into NPD injections are
very similar and differ both from the RO into RO and NPD into RO. The strongest effect is
detected for the NPD into RO. These results means that the mixings of NPD-RO solutions do not
behave like simple mixing of two solutions made from agents A and B that are not interacting.
This being the case one would expect that the results for mixing B into A and A into B be similar
and that these cases that involve increase in entropy (entropy of mixing) be different from the
neutral mixing A into A and B into B. keeping this in mind, we propose that the results of the
NPD and RO mixing involve more complex kinetics than mixing. More specifically, we suggest
that the results are consistent with the assumption of network of nanoparticles and nanobubbles
and long range order in the NPD solution for the following reasons: 1. The endothermic change
in the NPD into RO injection relative to RO into RO is consistent of distraction ("melting") of
the order in the NPD that absorbs heat. 2. One would expect that in the opposite case of RO into
NPD relative to NPD into NPD the formation of order in the small droplet of RO should show as
exothermic change. We propose that there is no change because of proximity effect – the order in
the bulk NPD solution in the cell induces order in the small amount of RO solution in the
injecting syringe that is immersed in the NPD solution. We note that a proximity effect of
induced long range order was reported in (20). 3. We propose that the difference between
injections into RO solution and injections into the NPD solution (more exothermic in the later
case) is connected with modifications induced in the order caused by the mechanical process of
the injections. Such modifications are equivalent to excess heating (beyond the injections heating
that is always observed in A into A injections). Clearly additional detailed measurements using

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different size droplets, different injection times and comparison between results with and without
stirring need to be performed for substantiated conclusions.

Discussion and conclusions

We presented interesting observations (20) relating to the effects of RF-treatment on

electrochemical deposition and its stabilization by nanoparticles doping. We propose that the
previously reported anomalous effects of RF-treatments of water (1-12) together with the new
findings reported hint to the existence of overlooked physical phenomena related to the
fundamental properties of water – induced long range (dozens of microns) order that can last for
long time. It was suggested that external long-range order is generated by the formation of
network of nanobubbles that has a non arbitrary architecture. We specifically suggested that
bubble-bubble interactions lead to self-organization of the bubbles into a pliable network with a
hierarchical organization of clusters and clusters of clusters of nanobubbles, with larger bubbles
being the hubs of the clusters.

To further test the idea of induced long range order we performed CD measurements which
indicate that the NPD solutions have optical activity which is different from RO water, and ITC
measurements which indicate that the NPD solutions have lower free energy. Both results are
consistent with the existence of long range order. If correct, the idea has many far reaching
implications. Yet much additional experimental and theoretical efforts are called for to validate
and substantiate this new paradigm.

Acknowledgments

The research reported here has been supported in part by the Tauber Fund and by the Maguy-
Glass Chair in Physics of Complex Systems. We are thankful to Do-Coop Technologies Ltd. for
providing us with the nanoparticles doped water (NeowaterTM) and for technical assistance.

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