ELECTROPOLISHING

Prepared by: Paidpilli Mahesh kumar (08120034) Aurobindo Mahanty(08120013) Nirvesh Biswas(08120029)

An Introduction to Electrometallurgy by SHARAN & NARAIN

PROBLEM: With Mechanical Polishing
•The processes induce stress in the surface layer •Mechanical treatment can also be labour intensive •It involves microscopic scratches, strains, metal debris and embedded abrasives

Material and Applications series, Vol.6,(The Mechanical Finishing of stainless

SOLUTION: ELECTRO POLISHING
•An electro polished surface is completely featureless. •The grain boundaries smoothed edge to edge due to which the usual sites for stress cracking have been removed which enhance strength •It reveals the original crystal structure of the metal without the distortion produced by the cold-working process •Work hardening induces compressive stresses into the surface of the material. BY electro polishing can easily remove this work hardened layer

•This removal of discontinuities in the edges of the grain boundaries will also remove sites for chemicals, dirt and microorganisms to be trapped.
•The reduction of the total surface area of the grain boundaries exposed to the process which significantly reduces exposed to Material and Applications series, Vol.6,(The Mechanical Finishing of stainless chemical attack.

MM100

MM100

MM100 Material and Applications series, Vol.6,(The Mechanical Finishing of stainless

What is ELECTRO POLISHING? polishing Electro PRINCIPLE:

is a chemical surface-finishing technique by which metal is electrolytically removed, ion by ion, from the surface of a metal object. When current is applied, the electrolyte acts as a conductor to allow metal ions to be removed from the part. While the ions are drawn toward the cathode, the majority of the dissolved metals remain in solution. Some ions are deposited in sludge form on the cathodes The quantity of metal removed from the workpiece is proportional to the current applied, the efficiency of the electrolyte and the exposure Protection,, Vol 13A, ASM Handbook, ASM International, time

M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and

MECHANISM OF ELECTROPOLISHING:
The process is generally considered to include:
1. leveling (or smoothing) action 2. brightening action.
•The electrical potential of the power supply or potentiostat causes electronic conduction to the WE and CE and ionic conduction in the electrolyte. This may result in controlled anodic dissolution of the anode material and cathodic deposition on the CE of some species present in the electrolyte. •During the electrolytic process, a viscous liquid layer immediately adjacent to this surface is produced by the reaction between the metal and the electrolyte. This layer of solution, known as the polishing film As such, it controls the smoothing action. •The brightening action is related to the elimination of irregularities as small as approximately 0.01 μm and to the suppression of etching on the metal surface. This behavior is generally attributed to the formation of a thin, partly passivating film directly on the surface of the metal and following its contours
Int.J.Electrochem.sci.,4 (2009) p-238-246

ANODE FILM

•The electrochemical reaction is under diffusive mechanism. •Due to the diffusive mechanism, a viscous layer will be formed on the anode. With respect to the bulk of the electrolyte, one proposed by Jacquet this layer has higher viscosity and greater electrical resistivity. The thickness of the insulating layer is greater in crevices (α) than on projections (B).
Int.J.Electrochem.sci.,4 (2009) p-238-246

Lightning Rod Effect •Ben Franklin proved that a piece of material that is charged tends to have very pronounced concentration of charge at edges and irregular or sharp points significantly greater charge concentration on them as compared to the valleys of the work surface then the points in the metal with the greatest ionic charges will have a greater electromotive potential for ionization into solution •The rate of the electrochemical reaction is directly proportionate to the current density. The increased current density at the raised points forces the material to dissolve faster at these points and thus tends to level the surface.

Chemical Saturation Effect
This rapid increase of heavy metal ions into solution is what we believe creates the anode film. As the anode film becomes saturated with metal ions, the electro polishing process slows down or stops in response to the increase in the anode film Metal Ion Saturation Level. The Viscosity Effect: The electro polishing solution approaches its saturation point, its viscosity greatly increases this creates a stagnant layer of Saturated Electro polishing Solution or

The Osmosis Effect: The metal ions in solution at the edge of the "Anode Film" will naturally migrate into the main body of the electro polishing solution. This loss of ions into the main body of the solution reduces the ion saturation of the electro polishing solution at the surface of the anode film. This results in the outer layer of the anode film becoming more active than the inner layer. This creates a situation where metal can still be removed in the regions of the anode film farthest away from the surface of the work piece Gas Mixing/Pump Effect: The oxygen is generated at the outermost edge of the anode film since this oxygen is generated as a gas, it will form bubbles and rise to the surface. This bubbling works as a pump and moves the main body of the electro polishing solution along the surface of the anode film. This movement causes the electro polishing solution to mix with the "Anode Film Solution" at the surface of the anode film. The mixing allows fresh electro polishing solution that is not at saturation to mix with the anode film and reduce its outer layer below the saturation point. Again, with the outer layer of the anode film active,

Anodic Processes
Anodic dissolution processes are complex. Depending on the nature of the dissolving metal (M), the electrolyte composition, and the current density, the following anodic (oxidation) reactions may occur:
•Transfer of metal ions into the electrolyte: Me → Me2+ + 2e•Formation of oxide layers: Me + 2OH-→ MeO + H2O + 2e•Evolution of oxygen: 4OH-→ O2 + 2H2O + 4e(Eq 3) (Eq 2) (Eq 1)

M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM International,

M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM International,

Original surface

•Some metal in ambient air is covered by oxide layer.
•Acid solutions of < pH(according to the Pourbaix diagram) dissolve this oxide,.

500x

CASEV,E.J.AND R.E.BERGERON(1953) The electrolytic polishing of metals.Can.Jour.Chem.31,422. M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM

Etched surface(Active dissolution) after treatment with less than critical voltage

At Anode: 2Me = 2Me(2+) + 2 e(-), At Cathode: 2 H(+) + 2 e(-) = H2 (gas).

500x

CASEV,E.J.AND R.E.BERGERON(1953) The electrolytic polishing of metals.Can.Jour.Chem.31,422. M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM

Indicating unstable conditions on the metal surface. This represents active-passive behavior.

Formation of viscous Electrolyte layer

CASEV,E.J.AND R.E.BERGERON(1953) The electrolytic polishing of metals.Can.Jour.Chem.31,422. M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM

Polished surface after treatment in the critical voltage range
At Anode: 2Me = 2Me(2+) + 2 e(-) After enough dissolved Cu(+2) is in solution At Cathode: Me(+2) + 2 e(-) = Me

The acid chemically dissolves any Oxide layer formed into solution by: MeO + 2 H(+) =Me(2+) + H20 500x

while new Oxide layer continues to form electrochemically on the high points of the anode Me+2OH(-) =MeO+H2O+2e(-)

CASEV,E.J.AND R.E.BERGERON(1953) The electrolytic polishing of metals.Can.Jour.Chem.31,422. M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM

Pitted surface after treatment above the critical voltage range

500x With excessive voltage ('overvoltage'), the diffusion and dissolution processes cannot keep up with the electrical current, and the excess current is expended in the dissociation of water, with O2(gas) formed at the anode per H2(gas) formed at the cathode.

CASEV,E.J.AND R.E.BERGERON(1953) The electrolytic polishing of metals.Can.Jour.Chem.31,422. M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM

Electro polishing by induction
The inductive method of electro polishing is useful in finishing certain types of surfaces which require polishing on only one side,
There is no direct electrical connection between the part and the circuit, current is induced in the sheet as the current flows. The side nearest the anode becomes relatively negative, and the side nearest the cathode, relatively positive, The positive side electro polishes, while the negative side does

Magneto electro polishing

(10um)

The MEP process involves performing the standard EP technique under the influence of a constant magnetic field.  In the EP process, an externally applied magnetic field works in two ways: the field either enhances or retards the dissolution rate of processed material.
T Hryniewicz, R Rokicki, and R Rokosz, “Magnetoelectropolishing Process Improves Characteristics of Finished Metal Surfaces,” Metal Finishing 104, no. 12 (2006): 26–33.

Atomic Force Microscopy (AFM) The dissolution rate depends on the strength of the applied magnetic field, but it is independent of the dissolved material’s magnetic properties and the electrolyte used.
In addition, a constantly applied magnetic field oriented parallel to the cathode surface during MEP suppresses hydrogen evolution. This minimizes the hydrogen embrittlement of magnetoelectropolished material. .

T Hryniewicz, R Rokicki, and R Rokosz, “Magnetoelectropolishing Process Improves Characteristics of Finished Metal Surfaces,” Metal Finishing 104, no. 12 (2006): 26–33.

PROCEDUR E:
The work must be performed in three major operations:
Metal Preparation

Electro Polishing

Post -Treatment

Material and Applications series, Vol.6,(The Mechanical Finishing of surface )

Metal preparation: To remove surface oils, greases, oxides and other contaminants that interfere with the uniformity of electro polishing

Metal Preparation

Cleaning

Rinsing

Pickling

Rinsing

Material and Applications series, Vol.6,(The Mechanical Finishing of surface )

Electro polishing: To smooth, brighten and/or deburr the metal

Electro Polishing

Electro Polishing

Drag-out/Neutralisation

Rinsing

Material and Applications series, Vol.6,(The Mechanical Finishing of surface )

Post-treatment: To remove residual electrolyte and by-products of the electro polishing reaction and dry the metal to prevent staining.

Post -Treatment

Acid Treatment

Rinsing

Hot Rinsing

Drying

Material and Applications series, Vol.6,(The Mechanical Finishing of surface )

Factors effecting electro polishingconcentration 1.Effect of

NOVEL CHARACTERIZATION OF THE ELECTROPOLISHING OFNIOBIUM WITH SULFURIC AND HYDROFLUORIC ACID MIXTURES*H. Tian + #, S. G. Corcoran *, M. J. Kelley +#, C. E. Reece+#Applied Science Dept., College of William and Mary, VA 23187, USA+Thomas Jefferson National Accelerator Facility, VA 23606,

2.Surface Conditions can result in less than optimum electro Base metal conditions that
polishing finishes include :
 The presence of non-metallic inclusions  large grain size

 During electro polishing, metal is removed, revealing these flaws.

3.Effect of area

Fig 8. I-V curves with different cathode areas, the blue curve is normal. Much small area of cathode let the green curve like a line
WEP65 Proceedings of SRF2007, Peking Univ., Beijing, China662

4.Effect of stirring speed 5.Effect of voltage confirming is difficultly polishing, but the temperature
 High stirring speed will lead high current density as well as high speed of

NOVEL CHARACTERIZATION OF THE ELECTROPOLISHING OF NIOBIUM WITH SULFURIC AND HYDROFLUORIC ACID MIXTURES* H. Tian + #, S. G. Corcoran *, M. J. Kelley +#, C. E. Reece+#Applied Science Dept., College of William and Mary, VA 23187, USA +Thomas Jefferson National Accelerator Facility, VA 23606, USA *Material Science & Engineering

6.EFFECT OF ELECTROLYTIC TEMPERATURE ON REFLECTION OF Al

Int.J.Electrochem.sci.,4 (2009) p-238-246

7.EFFECT OF ELECTROPOLISHING TIME ON REFLECTION OF Al

Int.J.Electrochem.sci.,4 (2009) p-238-246

Electro polishing of Why electro polishing of 316l steel ? stainless steel
How it To improve the surface layer consisting of corrosion-resistant chromium oxide works ?
 In the case of stainless-steel alloys such as 316L, iron and nickel atoms

are more easily extracted from the crystal lattice than are chromium atoms. That is, iron and nickel are attacked preferentially during the electrolytic process leaving behind an enhanced surface layer of chromium,
 which then forms the passive enrichment layer. 

This process Conditions : Operating also tends to smooth the surface finish ft2)dependent on alloy shape of article. used and : 10 to 20volts dependent upon the size of the density applied : 60 to 90` C (140 to 195`F).

 Anodic Current Density : 16 to 45amp / dm2 (150 to 400 amp /

 

voltage load,the current Temperature.

 Time. : 4 to 10 minutes. Comparing the characteristics of surfacepassivated and electropolished 316L stainless steel Patrick Lowery, Unit Instruments; and Daryl Roll, Astro Pak

ELECTROPOLISH FINISH STANDARDS (EFS) 1.Verification by SEM Photo microscopy
 Electro polisher to provide photomicrographs (100x

and1,000Xmagnification) of representative surface areas to assure maximum electro polished surface condition.
 Surface will show no evidence of grain boundaries.”

2.Verification by Auger Electron Spectroscopy
 Electro polisher to provide results of Auger Electron Spectroscopy

(AES) taken from representative surface areas to assure maximum electro polished surface condition. Depth of chrome oxide layer shall not be less than 20 Å (Angstroms)

3.Verification by ESCA Analysis
 Electro polisher to provide results of Electron Spectroscopy for

Chemical Analysis (ESCA) taken from representative surface areas to assure that the maximum electro polished condition has been achieved.  ESCA will be conducted in tandem with AES to confirm the quality of the Cr/Fe oxide profile
DELSTAR METAL FINISHING, INCESCA

SEM PHOTO MICROGRAPHS : The Proof of Quality Assured Electro polishing

S.S. Plate(1000 x)

Inadequate Electro polishing (1000 x)

Intermediate Quality (1000 Premium-Grade Electro polishing (1000 x DELSTAR METAL FINISHING, x)

Passivation vs. Electropolishing
Passivation
 Passivation does not change

Electropolishing
 This process also tends to

the appearance of the stainless
 Passivation is the process in

smooth the surface finish
 Electropolishing is the reverse

which a passive layer is created,which makes it inactive to environment.

of plating in that metal is removed from the surface rather than deposited Electropolishing also removes burrs and sharp edges; removes stress from springs and stampings by removing microscopic nicks and scratches from the surface.

Selection of Electrolytes
The ideal electrolyte for electro polishing must: Provide high quality polishing at low voltages and current densities Have the ability to function over a large range of current densities and temperatures Offer stability and long service life

Not dissolve the metal when no current is flowing; that is, no spontaneous corrosion occurs
Be inexpensive, readily available, and safe

Be recyclable
Have an ohmic resistance (IR drop) that is sufficiently low to obtain the desired current density at low voltage

M.

Provide good throwing power; that is, a sample with complex geometry should Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, Testing, and Protection,, Vol 13A, ASM Handbook, ASM International, dissolve uniformly over the entire surface

Material Aluminium alloy

Electrolyte 25-30% HNO3 in Methanol

Condition 5-7 V DC: -30C

Copper Alloy

70% orthophospheric acid and 30% water 20 wt% KCN in water 1)25% perchloric acid(70%) in glacial acid 2) 2% perchloric acid in 2butoxyethanol. 12%H2SO4 in water 2%perchloric acid in 2butoxyethanol 10%HF in HNO3 80%NaNO3, 20%NaCl 15%H2SO4 in methanol

16V DC: copper counter electrode 4-5 V DC 10-25 V DC

Gold Iron alloy and steels

10-25 V DC 6V DC 25 V DC

Molybdenum Nickel alloy

Niobium Platinum Vanadium

1-3 V DC 3-5 V DC: molten 6.5 V DC

Atom probe tomography: analysis at the atomic levelBy Michael Kenneth Miller

Properties of Electropolished Surfaces:
The physical, corrosion, and mechanical properties of a polished metal surface depend on the nature and the surface state of the metal . Mechanically polished surfaces may have an amorphous or mechanically deformed layer that influences its corrosion behavior. However, this layer is gradually removed to the crystalline structure during electro polishing. Effect of Electro polishing on Properties of Metals . In general, some of the mechanical properties of electro polished surfaces, such as hardness and Young's modulus, are increased. Mechanical polishing produces a cold-worked surface layer that generally enhances the fatigue life of metals. Fatigue life may be reduced when this layer is removed by electro polishing. On the other hand, surface roughness of the metal is reduced, which may increase the fatigue life of steel .Stress concentrations are also reduced.

Magnetic properties of steel alloys are altered when the cold-worked layer is removed by electro polishing . Surface conductance is improved. The effect of electrolytic polishing on the corrosion Testing, and Protection,, Vol 13A,depends onASM International, M. Ziomek-Moroz, Electro polishing, Corrosion: Fundamentals, properties of metals ASM Handbook, the post-

Safety Precautions:
Generally, the chemicals and combinations of chemicals used in electro polishing are poisonous; many are highly flammable or potentially explosive. Only well-trained personnel who are thoroughly familiar with chemical laboratory procedures should be permitted to handle or mix the chemicals or to operate the polishing baths .
Mixtures of HClO4 and acetic anhydride are extremely dangerous to prepare and are even more unpredictable to use. These mixtures are highly corrosive to the skin, and the vapors of acetic anhydride can cause severe damage by inhalation. These hazards are considered sufficient reason for recommending that mixtures of HClO4 and acetic anhydride not be used, despite their effectiveness as electro polishing electrolytes. Electrolytes must be discarded immediately after use by flushing down a chemical waste drain with a large amount of water. Mixing, storing, and handling of electrolytes should be done using containers and equipment made of materials suitable for the chemicals used. Glass is resistant to nearly all chemicals.
ASM Handbook - Vol 09 - Metallography and

APPLICATION:
1.The Aerospace Industry The aerospace industry is one in which high reliability and flawless quality are a matter of life and death. •Turbine blades •Engine parts •Vacuum chambers •Piping and tubing systems •Landing gear parts •Doors 2.Automotive Industry In the automotive industry, improved quality has become a major competitive factor. Parts need to be durable, reliable, and resistant to corrosion.

APPLICATION:(contd.)
3.Food and Beverage Industry In the food and beverage industry, ease of cleaning and the maintenance of sterile and sanitary surfaces are critical. 4.Medical and Dental Applications Electro polishing metal objects for medical and dental purposes provides both short term and long term benefits Some of the objects that should be electro polished for medical use include: •Surgical equipment such as scalpels, clamps, saws •Prosthetic devices, bone and joint implants •Tubing, needles

APPLICATION: (contd.)
6.Petrochemical Electro polishing will also result in increased heat transfer efficiency in heat exchangers, enhanced flow characteristics in piping and tubing, and the elimination of burrs from machined parts. Commonly electro polished parts in the petrochemical industry include: •Reactor Vessels •Heat exchangers •Mixers •Storage tanks

5.Water Purification In the semiconductor industry, for example, water needs to be extremely pure in the manufacturing of microchips. Without undergoing the electro polishing process, water purification systems may take six weeks just to achieve the level of purification necessary

Benefits of Electro polishing:
 Increased resistance to corrosion.  Improved Surface finish.  Reduced product Adhesion & Ease of cleaning.  Deburring.  Less Time consuming.  Attractive appearance.  Lesser Cost.

Benefits of Electro polishing:(contd.)
 Reduction of the total surface area of the grain boundaries exposed to the process. This significantly reduces the amount of material from the grain boundary areas exposed to chemical attack.  This removal of discontinuities in the edges of the grain boundaries will also remove sites for chemicals, dirt and microorganisms to be trapped.  In the areas of high vacuum work, the smoothing effect is useful because it effectively reduces the total process surface area of the work piece. This reduces the gas load on the system allowing one to reach higher vacuums more easily.

 Electro polishing is particularly well suited to softer metals, which may be difficult to polish by mechanical methods. Scratching does not occur in electrolytic polishing. The absence of scratches is advantageous in viewing high-quality electro polished surfaces .

DISADVANTAGES OF ELECTROPOLISHING
 Electro-polishing Difficult for Some Metals. Not applicable to gray cast Iron. Critical Adjustment of Terminal Voltage for some metal is required

Removal of Non metallic Inclusions.
Only metal is removed from the surface. Defects such as casting porosity are made more evident. This can be advantageous in identifying faulty jewellery. It will remove very small defects (1-2 microns) but not larger defects. The conditions and electrolytes required to obtain a satisfactorily polished surface differ for different alloys. Consequently, considerable time may be required to develop a procedure for a new alloy.

Metallographic preparation by electro polishing is subject to several limitations, which should be recognized to prevent misapplication of the method and inappropriate results
In multiphase alloys, the rates of polishing of different phases often are not the same and preferential attack may also occur at the interface between

THAN KYOU