The effect of Rf-irradiation on ECD –A manifestation of induced long range order?

Y.Katsir (1)(2)(*)($)
, L.Miller (3)(*)
, Y.Aharonov , E.Ben-Jacob
(1) (1)

The effects of RF-irradiation of water The protocol

During the past two decades, much effort has been devoted to study the long term (hours) 1. We performed ECD experiments in control solutions, solutions that where treated by RF-irradiation
effects of rf-treatment on the properties of water and aqueous solutions (1-3). The following are before the ECD process and in solutions made from NPD-water.
some examples of well documented effects: 1. Formation of stable gas nanobubbles. 2. We monitored the pattern on the macro-scale and used HR SEM and SEM to study the micron-level
2. A decrease in surface tension from 72 to 68 dyn/cm. 3. Increase in the intensity of all three organization of the deposits.
infra-red (IR) spectroscopy frequency bands. 4. Increase in the concentration of atomic 3. The RF-irradiation was at 915 MHZ , for about 20 minutes and about 10W power while keeping the
hydrogen. 5. Modifications in the spectra of dissolved hydrophobic fluorescent molecules. water at fixed temperature.
6. Changes in the zeta potential.
It was proposed that the effects are due to water ordering induced by the gas bubbles. Here we test
.(this hypothesis by study of the effect of RF-treatment on Electro-Chemical-Deposition (ECD) (1 The experimental findings
Control Rf-treated solutes
NPD-water

Electro-Chemical-Deposition in Circular Cells

ECD of metals in thin gap geometry has been widely used over the last twenty years to
study the foundation of pattern formation and self organization in open systems far
from equilibrium. A great variety of macroscopic patterns (morphologies) are formed
as a function of several control parameters: applied voltage, initial concentration,
chemical composition of the solutions, its viscosity etc.

The circular ECD cell The typical Morphology Diagram

DBM Induced Morphology Diagram: For some growth conditions that dendrites are grown in
the control solution, DBM morphology is generated in the RF-treated solutions and in the
solutions made from NPD-water.
Dendrites

Micro-Macro interplay and Morphology Selection in ECD:

Measurements on all scales from micro-level structures (using electron microscopy and
X-rays) to the macro-level patterns played a crucial role in establishing the theoretical
framework about the micro-macro singular interplay reflected in the morphology
selection and morphology transitions. In this regard the ECD process provides a probe 50µm 50µm
of micro-level effects.
SEM observations of the effect on the DBM: .(These results are at lower voltages (8V

(Nano Particle Doped water (NPD-water

HR SEM TEM
Sub-micron hot (900)
source powder is dropped
into RF-irradiated water
kept below the anomaly
temperature. The process
leads to the formation of
spherical particles The effect on Dendritic growth: .(These results are at higher voltages (13V

Source powder The processed particles

We propose that our findings together with the previously reported anomalous effects
(The NPD-water used here is the Neowater (5 of RF-treatment hint the existence of new physical phenomenon – The formation of
that has about 10 12 particles per 1ml Nanobubble Networks

– Nanobubbles stability Bubble-Bubble Formation of The effect of

The New paradigm Exchange Interactions Nanobubble Networks Nano particle doping
Experimental proof using AFM
It has been proposed before that 2. The exchange interactions lead The networks induce long .3
:We propose that to the formation of nanobubble .range order
(1) The nanobubbles have long-term networks with hierarchical In NPD-water nanoparticles act .4
1. The induced order around
stability (hours); organization. With larger bubbles as the hubs leading to
each of the nanobubbles
being the hubs of the network. stabilization of the nanobubble
mediates bubble-bubble
(2) The gas-water interface of the .networks
exchange interactions.
nanobubbles is hydrophobic and
Bubble Particle
therefore the water molecules form
clathrate shells with an “ice-like”
structure around the gas
nanobubbles;
Direct observations of nanobubbles on
(3) The ordered shells can induce
hydrophobic surfaces using liquid atomic force
order in the water molecules
microscopy in high resolution tapping mode (4).
surrounding the nanobubbles that
The observations revealed that once formed, the
extends up to a micron in range.
nanobubbles can be stable for hours. (Picture is Nanobubbles Nanobubbles
thanks to P. Attard ref(4 ))

Affiliations
Testing the New paradigm (3)School of Physics and Astronomy, Tel Aviv University, Tel Aviv 69978, Israel (2)
Current address: Department of Chemistry Bar Ilan University, Ramat Gan 52900,
As a step in this direction, we used Isothermal Titration Calorimetry (ITC) to test the effect of injecting Israel
solutions made with the NPD-water into control solutions and vice versa. The preliminary results show an (3) Department of Materials Engineering, Technion, Haifa 3200, Israel
endothermic peak in the former case, implying that the NPD-water solutions have lower free energy, which is (*) These authors have equal contributions
consistent with the hypothesis about induced long range order (1). ($) Presenting author

Subtraction of ZN -> ZN Subtraction of

ZN in NPD ->ZN in NPD References
(1) Y. Katsir*, L. Miller*, Y. Aharonov and E. Ben-Jacob, The effect of rf-irradiation on
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electrochemical deposition and its stabilization by nanoparticle doping J.

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Electrochemical Society (accepted 2007). (*) these authors have equal contributions.
(2) For definition of water formatics see “Exploring water complexity” in: http://
star.tau.ac.il/~eshel/
(3) M. Colic and D. Morse, Physical Review Letters, 80, 2465 (1998)
(4) P. Attard, Advanced in Colloid and Interface Science, 104, 75 (2003).
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(5) The NPD-water is NeowaterTM provided by Do-coop Technologies Ltd.
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