Manufacturing Processes

(ME 361) Lecture 14

Instructor: Shantanu Bhattacharya
Electrode
surface
The Electrode Double layer
•For the case of an electrode dipping into a solution of
an electrolyte, the total charge on the electrode surface
must balance the total solution charge (opposite
charge).
- + •There is an electrostatic interaction between the
electrode charge and solution charge.
•Ions from the solution may approach the electrode
- + surface only so far as their inner solvation shell.
•The surface array of the ions is thus cushioned from
Outer
Helmholtz
the electrode surface by a monolayer of solvent.
Plane

•The line drawn through the center of such ions at this distance of closest
approach marks a boundary known as the outer Helmholtz plane.
•The size of the ions forming the outer Helmholtz plane are larger and the total
no. of ions needed to do a complete charge balance cannot be all fitted on this
plane.
•The remaining charges are all held with increasing disorder in the outward
direction into the solution. This layer is known as the diffused part of double layer.
Electrode
surface The Electrode Double Layer
•The variation of the potential Ψ, with distance from the
electrode surface is shown in the figure below.
•Thus all the charge which neutralizes that on the electrodes
- + is held in a region between the outer Helmholtz plane and
the bulk of the electrolyte solution.
•This situation is very similar to that in Debye Huckle theory
- for 3-D in a ion solution.
+
•In the case of the planar electrode only 1-D needs to be
considered (normal to electrode surface)
Outer
Helmholtz
Plane

Ψ0
As x ∞ , Ψ 0

X
Electrode
surface
Capacitance Modeling of the diffuse layer

•There are effectively two components which make up

the total potential drop across the interface; Ψ0
Across the diffuse part and Ψ-Ψ0 across the fixed part.
- + •The total capacitance of the double layer, C, is made up
of that due to the inner layer, which we may designate
CH and that due to the diffuse layer CD
- +

Outer
Helmholtz
Plane

Ψ0

X
 Mass transfer and electron exchange process
•In considering the electron exchange reactions at electrodes we are concerned
essentially with the layer of solution very close to the electrode surface.
•There should however be some means available for the oxidant or the reductant to
reach the electrode surface.
•There are a number of ways that this can occur under the general heading of mass
transfer processes. They are:

1. Migration: The movement of cations or anions through a solution under the

influence of an applied potential between electrodes placed in that solution.
2. Diffusion: An electrode reaction depletes the concentration of oxidant or
reductant at an electrode surface and produces a concentration gradient there.
This gives rise to the movement of species from the higher to lower
concentration. (It occurs in both charged and uncharged species.)
3. Convection: This includes thermal and stirring effects which can arise
extraneously through vibration, shock and the setting up of temperature
gradients.
 Electrochemistry of ECM process

•When a metallic body is submerged in an electrolyte, the metallic atoms leave the
body and become ions and the ions move to the body and become atoms.
•The process goes on continuously and an equilibrium is maintained.
•A potential difference exits between a point on the surface of the metallic body
and an adjacent point on the electrolyte. This potential difference is known as the
electrode potential.
•The electrode potential varies depending on the electrode-electrolyte
combination.
•If two different electrodes A and B are immersed, a potential difference between
these two electrodes will exist since the potentials of A and B are different with
respect to the electrolyte.
 Electrochemical Machining
•This potential difference is the
electromotive force of the cell,
generated by the electrodes and
the electrolyte.

•If Fe and Cu electrodes are

dipped in brine (solution of
kitchen salt in water) the
electrode potentials are the
following:

Fe = Fe+2 + 2e- ---------------- -0.409V

Cu = Cu+2 + 2e- ---------------- 0.304V

Difference between electrode potentials = 0.713V

The nature of the electrolysis process depends on the electrolyte used. To, understand
how ECM is realized, let us consider the aqeuous solution of sodium chloride as the
electrolyte. When a voltage difference is applied across the electrodes, the reactions at
the anode and the cathode are the following :
 Electrochemical Machining
• Reaction at the anode:
Fe ------- Fe+2 + 2 e-

• The electrode metal Fe dissolves, leaving 2

electrons.
2H2O + 2 e- -------- H2 + 2 (OH)-
The water gets two electrons from the electrode
and , as a result, the hydrogen gas is evolved and
hydroxyl ions are produced.
 Electrochemical Machining
• Then, the positive metal ions combine with the negatively charged
hydroxyl ions to form ferrous hydroxide as:

Fe+2 + 2 (OH)- ------ Fe(OH)2

• The ferrous hydroxide forms an insoluble precipitate.
• So, with this kind of electrode metal-electrolyte combination, the
anode dissolves and H2 generates at the cathode, leaving the
cathode shape unchanged.
• This is the most important characteristic of the electrochemistry of
the ECM process.
• It should be noted that for ECM the choice of electrodes and the
electrolyte must be such that no deposition at either electrodes can
take place.
 Electrochemical Machining
• The gram equivalent weight of the metal is given by ε = A/Z, where A is the atomic
weight and Z is the valency of the ions produced.

•The rate of mass removal is given by:

m = AI/ZF

If density of the anode material is ρ, the volumetric removal rate is given by

Q = AI/ ρZF cm3/ sec,

Where
A = gram atomic weight of the metallic ions,

I = current (amperes)

ρ = Density of the anode (gm/ cm3 ),

Z = valency of the cation,

F = 96,500 coulomb
 Anode made of Alloy
•When the anode is made up of an alloy instead of pure metal, the removal rate can be
found out by considering the charge required to remove an unit volume of each element.

• If the atomic weights and the valencies of corresponding ions entering the electrolyte are
A1, A2, A3……. and Z1, Z2, Z3…….. Respectively, and the composition by weight of the alloy
is x1% of element 1, X2% of element 2,……., then a volume v cm3 of the alloy would
contain vρxi/ 100 gram of the i th element, where ρ is the overall density of the alloy in
gm/ cm3 . The charge required to remove the ith element in volume v is given by:

(v ρ xi/ 100). (Zi F/ Ai)

The the volume of the alloy removed per unit charge is

Q = (100/ ρF) ( 1/ Σ(xiZi/ Ai)) cm3/ amp-sec or

Q = [(0.1035 X 10-2)/ ρ] ( 1/ Σ(xiZi/ Ai)) cm3/ amp-sec

 Numerical Problems
In an electrochemical machining process
with a pure iron work-piece, a removal rate
of 5 cm3/ min. is desired. Determine the
current required.
 Numerical Problem
•In the actual ECM process, there are many other
factors which affect the removal rate.
•The process is seldom as ideal as we have described.
•The actual removal rate may vary slightly from that
obtained theoretically from equation for Q

•The theoretical and the actual removal

rates with nickel as work material are
shown in the figure and they vary slightly.
•The reason is that the theoretical removal
is based on Divalent dissociation.
 Voltammetry (Linear Sweep and Cyclic)

•The above two techniques involve the application of a linearly varying potential between
the working electrode and a reference electrode placed in an electrochemical cell
containing a high concentration of an indifferent conducting species and an oxidizable
and reducible species.
•The current through the cell is monitored continuously and a graph is traced between
the current and the potential.
•This is known as a voltammogram.
•The most straightforward technique is known as linear sweep voltammetry.
• At start point A the current is very
small.
•Between A and B it rises very slowly
owing to the residual current (from
impurities and double layer charging
effect). This is sometimes called the
background current.
•At point B the potential approaches the
reduction potential of the oxidized
species (Ox).
•The increasing potential causes the
Ox + ne---------- R electrons to transfer from the electrode
to the Ox.
 Multivalent dissociation
•So, as the current is more, i.e., the dissolution takes place at a higher potential
difference, trivalent dissolution also occurs.
•Therefore, at larger currents the theoretical values tend to be more than the actual
ones.
•Sometimes the dissolution valence also depends on the electrolytes. (For eg.: Copper
dissolves in mono-valent form in chlorine solutions, whereas in nitrate solutions, the
dissolution takes place in divalent state.
•The table on left shows some imp. Data on some
elements
 Numerical Problems
The Composition (%) weight of the Nimonic 75 alloy is given here:

Calculate the removal rate (in cm3/min.) when a current of 1000 amp is passed. Use the
lowest valency of dissolution of each element.
Numerical Problems
Numerical Problems
 Electrochemical Machining
•The relationship between the voltage applied across the electrodes and the flow of current
is not very simple.
•The total potential profile consists of the following:

1. Electrode potential.
2. Overvoltage due to activation polarization. The electrochemical changes are in
equilibrium when no current flows. The electrode potential acts as a barrier to a faster
rate of reaction. So, an additional energy has to be supplied to get the required mrr.
3. Concentration polarization. The ions migrate towards the electrodes of opposite
polarities, causing a concentration of ions near the electrode surfaces.

Each ion must pass through this concentration

barrier to release its charge at the electrode.
4. Ohmic Overvoltage: The films of solid
materials forming on the electrode surface offer
an extra resistant to the passage of current.
5. Ohmic resistance of the electrolyte: The
ohmic voltage drop occurs across the bulk of the
electrolyte. This is the main voltage drop and is
the only part of the electrolyte obeying Ohm’s
law.
 Electrochemical Machining
•If the total overvoltage at the anode and the cathode is ΔV and the applied voltage is V,
the current I is then given by:

I = (V- ΔV)/ R

Where R is the ohmic resistance of the electrolyte.

•The conductivities of the tool and the workpeice are much larger than the conductivity of
the electrolyte.

•The typical electrolyte conductivity is around 0.1-1.0 Ω-1 cm -1 , whereas that of iron is 105
Ω-1 cm -1 .

•Thus the surfaces of the tool and the workpiece can be considered as equipotential.

•The conductivity of the electrolyte is not really constant because of the temperature
variation and accumulation of the bubbles.