chemical surface preparation

ELECTROCLEANING
BY NABILZAKI
SUR-TEC GMBH, ZWINGENBERG, GERMANY;www.surtec.corn

Electrocleaning is a cleaning process used in metal surface preparation, usually

in preplate cycles. It is essentially characterized by the use of DC current and a spe-
cially formulated electrolyte. The work being processed may be used as anodes or
cathodes, or both, depending on the application. Although electrocleaning is a
different and distinct method of surface cleaning, it should be considered in the
context of the complete surface preparation or preplate cycle. Such a general cycle
might include: (1) soak clean, (2) rinse, (3) electroclean, (4) rinse, (S) acid activate,
(6) rinse, (7) repeat steps 3 to 6 (optional), and (8) plate.
Electrocleaners as described here are alkaline and will generally follow alkaline
soak cleaners and precede acid activation in the preplate cycle. The basic function
ofelectrocleaners is to remove soils from the surface that could not be removed
by simple immersion soak or degreasing steps. Examples of such soils are as fol-
iows~
Adherent residues not removed in the preceding soak cleaner. Such residues
include oil, fingerprints, drawing compounds, and soils driven into surface
porosity or applied under pressure. These soils are not generally removed by con-
ventional emulsification, wetting, and displacement soak cleaners.
Finely divided particles, such as polishing compound abrasives, metallic fines
from grinding or metalworking operations, carbon, and other alloying elements,
may also be found on the surface. Often this fine particulate matter, generally
referred to as smut, may be held to the surface by simple mechanical forces, elec-
trostatically, or in a thin oil or grease matrix.
Metal oxidation products, the result of exposure to the atmosphere, or a
thermal process such as heat treatment, forging, welding, etc.
As explained earlier, electrocleaning must be viewed as part of the overall
surface preparation process. Although an electrocleaner step may not totally
remove a particular type of soil, it conditions or modifies that soil for easier
removal in the subsequent steps in the cycle. For instance an adherent oil residue
may be loosened enough to be lifted in the following rinse tank. Surface oxides
may be reduced or oxidized to a more soluble form to be easily dissolved in the acid
tank.

ELECTROLYSISOF ELECTROCLEANERS
As current is applied to an electrocleaner, the following electrochemical reactions take
place, essentially electrolyzing water. The alkalies serve as the conductive medium.
At the anode:
4OH- 2H20 + 02 + 4e-
At the cathode:
4H20 + 4e" 4OH" + 2H 2
As can be seen, twice as much hydrogen is liberated at the cathode than is oxy-
gen at the anode.

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TYPES OF ELECTROCLEANERS
Electrocleaners are classified on the basis of two main interrelated criteria: (1)
polarity of the work in the tank; (2) type of substrate being treated.
There are three types ofelectrocleaning modes as defined by polarity of the work
in process and the applicability of each to a given substrate.
Anodic Electrocleaning
The work is connected to the anode side of the rectifier and is positively charged.
The process is also known as reverse electrocleaning, since the polarity is opposite
that of plating. As described under electrolysis, oxygen is liberated at the surface of
the work (the anode) when current is applied. As the gas rises to the top, it creates
a mechanical scrubbing action that loosens and lifts the soils.
Two other phenomena also take place. As oxygen bubbles are formed on the sur-
face, they coalesce and grow before they rise in continuous layers. It is believed that
the static charge holding fine particles to the surface is released through the layer
of bubbles, facilitating their removal through the scrubbing action.
Chemical effects, oxidation, and drop in pH also take place at the anode surface.
If excessive, the effect of oxidation can be seen, for instance, on brass, zinc, and sil-
ver as they discolor, stain, or etch. Special inhibited anodic electrocleaners are
available for brass and zinc.
When nickel is anodically electrocleaned it will quickly passivate and prevent fur-
ther plating unless reactivated. A similar effect is experienced with stainless steels.
Regular steels are not adversely affected by the process, whereas high carbon steels
are more sensitive and require moderation in electrocleaning. Alloys of lead, nick-
el-silver, and silver plate are attacked or tarnished by anodic electrocleaning.
As oxygen is liberated at the anode, the net pH value tends to decrease at the inter-
face. This effect can be noticed on steel if an electrocleaner's alkalinity is too low by
design or for lack of bath maintenance. The steel is more rapidly oxidized, and pre-
cipitated iron hydroxide forms on the surface. Parts exiting the tank will have a rusty
or etched appearance, especially in high current density areas. The situation can be
readily rectified by increasing the alkalinity of the bath or by reducing the current
density below normal operating levels.
Cathodic Electrocleaning
The work is connected to the cathode side of the rectifier and is negatively
charged. This is also known as direct electrocleaning. In this case, hydrogen is lib-
erated at the cathode. As seen from the net amount of electrolysis, twice as much
hydrogen than oxygen is generated at the cathode. Consequently, more scrubbing
action and cleaning ability are expected. The use of cathodic electrocleaning,
however, has not found a widespread use in the industry as the main electro-
cleaning mode for two reasons: (1) the concern with hydrogen embrittlement as
a result of copious hydrogen release at the surface, and (2) the risk of plate out of
charged impurities from the solutions on the cathodic surface. The latter may not
be noticeable to the casual observer as the parts exit the tank, but leads to poor
adhesion on plating. Contaminants leading to such adhesion failures are metal-
lic fines, certain types of surfactants, colloids, metallic soaps, and hexavalent
chromium dragged into the cleaner.
Cathodic cleaners, when kept clean and well maintained, are used for process-
ing buffed brass, zinc, and white metal without tarnishing, and for electrocleaning
nickel and high nickel steels without risking passivation. When used on steel and

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Table I. Recommended E|ectrocleaning Current Densities~Rack Appfications
A/dm ~ Polarzty
Steel,lowcarbon 5-10 A,C
Steel,high strength 3-5 A
Stainlesssteel 5-8 C
Copper 5-8 A,C
Brass 2-4 A,C (anodicinhibited)
Zincdiecast 2-4 A,C (anodicinhibited)
Nickeland alloys 2-3 C
Leadand alloys 5-8 C
Silverand alloys 2-3 C
qn barrelapplications,a fractionof the abovecurrentdensityvaluesshouldbe expected.

copper, to take advantage of their superior scrub-clean action, a secondary anod-

ic electrocleaner should follow even for a few seconds. This step will deplate any
impurities that may have plated on the work by cathodic action.
PeriodicR~erse Elec~rodeaning
This method of electrocleaning of ferrous metals uses a combination of both
anodic and cathodic cleaning modes. A periodic reverse (PR) unit is installed on the
rectifier's output. The PR unit has a switching mechanism that reverses the polar-
ity at controlled and timed intervals. The work in the tank assumes alternating anod-
ic and cathodic polarities for the specified cleaning time.
Typical settings include 10 sec cathodic then 10 sec anodic, etc. By changing the
setting, more cathodic or anodic may be used to effect maximum cleaning. The
unit can be programmed so that the last leg of the cycle is anodic before the timer shuts
off the rectifier. This ensures removal of any charged particles that may have plated
on the work during cathodic cleaning.
The continuous oxidation and reduction at the surface converts the oxides
and scales on parts to more soluble forms that are picked up by cyanide or chelat-
ing agents built into the cleaner formulation. PR cleaners eventually become sat-
urated with dissolved iron oxides and must be replaced. Where practical, they
can be regenerated by plating out the iron cathodically. PR cleaning is very efficient
in descaling and derusting high strength and spring steels without the use of
acids in the cycle, thereby eliminating or minimizing hydrogen embrittlement.

O P E R A T I N G P A R A H E T E R S A N D PROCESS C O N S I D E R A T I O N S
Electrolysis is the main driving process in electrocleaners. The a m o u n t of gassing
responsible for the scrubbing action at the electrodes is a function of the a m o u n t
of current passing through the cell. Therefore, parameters controlling current
should be considered.
Solution Conductivity. This in turn is a function of cleaner concentration and
temperature at a given voltage. The higher the concentration and temperature (up
to a practical level), the higher the conductivity and the a m o u n t of gassing.
Voltage Applied. Current increases with voltage, although the latter is kept to
maximum values of 10 to 12 V. Higher values are known to cause "burning" or
roughness on parts.
Surface Area Being Cleaned. This parameter controls current density and, for a
given rectifier setting, will directly affect the cleaning efficiency.

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TaMe II. Typical Operating Conditions for Electrocleaning
Steeland Copper Brass Zinc Nickel and
Chromium Alloys
Alkalinity(as NaOH),g/L 50-100 15-20 15-20 30-60
Temperature, C 60-90 50-70 50-70 50-80
Time,min. 1-5 1-3 1-3 1-S

Adequate recommended current density ranges for different basis metals are sum-
marized in Table I. Values below these produce light to marginal electrocleaning.
Higher values generally lead to etching and roughness of the surface.
Anode to cathode area ratios of 1:1 are adequate for most applications. The ratio
is not critical as long as the specified current density values are maintained.

PROCESS C O N S I D E R A T I O N S
There are general considerations in the selection and proper use ofelectrocleaners.
Electrocleaner Formulation
Several proprietary formulations are available covering a wide range of applications.
These formulations should provide the following properties.
A suitable degree of alkalinity for the metal processed, e.g., high alkalinityfor steel,
lower for zinc and brass.
A proper ratio of hydroxide to silicate to prevent insoluble silicate films from
adhering to the work and affecting plate adhesion. Silicates are often used to pre-
vent burning of steel at high current density. Nonsilicated cleaners, using different
types ofinhibitors, are also available. Water softeners and conditioners should be
considered in hard water areas.
An adequate amount of wetting agent and emulsifiers. Although high lev-
els serve as cleaning agent for excess oil and grease, they inhibit the gassing
action at the electrode surface and reduce desmutting characteristics. Efficient
desmutting electrocleaners will have just enough surfactants to reduce solution
surface tension and promote a thin foam blanket to hold down gas misting dur-
ing electrolysis. Bulk oil removal should be a reserved function of the preced-
ing soak cleaner.
Typical operating conditions of electrocleaners are given in Table II. Suppliers
of proprietary electrocleaners usually tailor the parameters to specific applica-
tions, which may vary from the values shown in Table II. Alkalinity figures
expressed as NaOH may represent 20 to 80% of the total product formulation.
Process Control
Control of electrocleaners is usually done by titration of the alkali contents.
Maintenance additions will replenish alkalies, as well as surfactants and other
components included in the formulation.
Although the essential components can be maintained, contaminants build
up and eventually interfere with the proper performance of the bath. Oils and
grease, if not adequately removed in the preceding soak cleaner, may result in water
breaks out of the electrocleaner tank. Grease etch is also a result of such a
buildup. It shows as jagged etch spots after plating. It is due to uneven current
distribution around nonwetted spots on the surface being electrocleaned.
Hexavalent chromium trapped in cracked rack coatings and dragged into the elec-
trocleaner is another source of contamination. This leads to drastically reduced
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Table IlL Common E|ectrocteaning Problems
Problems
Etching, tarnishing
Roughness
Haze under plate
Poor adhesion, blisters,
pitting of plate
Probable Causes
Too high a current density
Cleaner noninhibited for nonferrous metals
Wrong polarity
Temperature too high for nonferrous metals
Excessive oil in solution
Cleaner too weak causing "bums" on steel
Excessive current density in anodic cleaning, pulling
alloying elements to the surface. In cathodic cleaning,
depositing charged particles and smut on surface
Incomplete rinsing ofelectrocleaner
Cleaner temperature too high causing dry-on film
Cleaner too weak
Incomplete rinsing after cleaner
Inefficient soak or precleaning prior ro electrocleaning
Hexavalent chromium contamination
Cleaner too weak
Current density too low or too high
Cleaning time too low or too high
Reverse of intended polarity
Hexavalent chromium contamination
Insufficient rinsing after cleaning
Excessive oil/grease in cleaner

cleaning and haze under nickel plate.

Stripping chromium plated parts for rework in the process electrocleaner has a
similar effect. Hexavalent chromium contamination can be readily detected as the
cleaner turns yellow-orange and foaming seems to subside. Compatible chromium
reducers are used to counter this effect. They reduce the chromium to trivalent if
the cleaner is not heavily chelated and allow most of it to precipitate as the hydrox-
ide. The solution color changes to light green, indicating the reduction process has
taken place.
EquipmentMaintenanceand Operation
Corrugated or mesh steel can be used as anodes or cathodes to provide optimum
surface area and solution circulation. Periodic deaning of the anode/cathode is nec-
essary to remove plated-on smut, oxides, and other charged partides. Using the tank
as the anode or cathode is not recommended, as it leads to uneven current distri-
bution and a source for stray current. Many electrocleaning problems, such as under-
and over-cleaning, have been traced back to such a practice. A summary of common
problems is given in Table III.
Polypropylene or lined tanks are recommended for alkaline electrocleaners fit-
ted with steel, stainless steel, or Teflon heaters. Recirculating pumps are recom-
mended to prevent stratification and ensure overall homogeneity. It should be not-
ed that solution inlet and outlet must be located at two opposite diagonal top and
bottom corners of the tank for efficient solution movement.
Cleaner filtration is gaining in popularity with the aim of prolonging the bath
life between dumps. Several filtration techniques have been proposed, ranging from
simple bag filtration to complete systems ofoil skimmers, coalescers, and ultra-
filtration. Since the cost of such systems varies appreciably, a feasibility study
must be undertaken before adopting a particular system. In general, however, it has
been reported that any type of filtration does increase the bath life at least by 20%

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and up to five times or more.

LIQUID CLEANERS
The use of liquid deaners to replace powders has been gaining momentum and wide
acceptance in the industry. These new cleaners are formulated to economically pro-
vide all the performance criteria of the powders. The advantages of liquid cleaners
include the capability ofantomatic feeding tied to conductivity controllers. The auto-
mated system continually monitors the solution strength and makes additions on
demand. Consequently, better bath control is achieved, eliminating wide swings in
concentrations. Automatic recording capabilities of concentration and temperature
can be achieved for statistical process control.
Tank additions of liquid concentrate eliminate the hazards associated with
additions of alkaline powders to hot cleaner solutions. As a result of better con-
trois, these liquid systems have substantially increased bath life in many instal-
lations.
Another advantage confirmed by users of liquid cleaners is sludge reduction
on waste treatment by 70 to 80%, which adds to the economical advantage of these
systems.

ELECTROCLEANING OF STRIP AND WIRE COILS

Strip and wire are continuously fed through the line. There is no direct contact with
anodes or cathodes in the electrocleaner tank. A bipolar electrical effect is used to
provide the polarity as follows. Two separate steel grids are positioned several
feet apart in the direction of work flow. The first grid is anodically connected, the
second, cathodically. The strip travels between two closely spaced jaws of each grid
without touching them. As a result of the bipolar effect, the strip assumes the oppo-
site charge of the grid. It becomes cathodic through the first grid, then anodic
through the second, achieving the desired electrocleaning effect.

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