Transactions of the IMF

The International Journal of Surface Engineering and Coatings

ISSN: 0020-2967 (Print) 1745-9192 (Online) Journal homepage: http://www.tandfonline.com/loi/ytim20

Pretreatment of aluminium for electrodeposition

Trevor Pearson

To cite this article: Trevor Pearson (2006) Pretreatment of aluminium for electrodeposition,
Transactions of the IMF, 84:3, 121-123

To link to this article: http://dx.doi.org/10.1179/174591906X114516

Published online: 18 Jul 2013.

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 Pretreatment of aluminium for
electrodeposition
Trevor Pearson*
Aluminium is a very useful material for
the production of both cast and
extruded fabrications due to its low
density and high strength to weight
ratio. A wide range of aluminium alloys
are available having an equally wide
range of mechanical properties.
Aluminium fabrications usually require
some form of finishing operation to
improve the appearance or corrosion
Downloaded by [University of Montana] at 22:59 09 February 2016
resistance. Anodising, chromating,
organic finishing and electroplating are
commonly carried out. Electroplating of
aluminium can be quite difficult to
accomplish successfully so it is the aim
of this paper to clarify some of the
issues and difficulties associated with
electroplating of aluminium.
Electrodeposition onto
aluminium substrates
Aluminium is an active metal that
reacts rapidly with atmospheric oxygen
forming a tenacious surface oxide layer
which effectively hinders adhesion of
applied coatings. Because of this
characteristic of aluminium, special
pretreatments have to be applied to
this material before it can be effectively
electroplated.1
Alkaline process solutions are most
effective at removing oxides from the
surface of aluminium because
aluminium oxide is more soluble in
alkali than acid. The process solutions
usually used for aluminium
preteatment are based on a solution of
sodium zincate. Aluminium is more
electrochemically active than zinc and
so when it is immersed in a solution of
sodium zincate, first the oxide layer is
removed then an immersion deposit of
zinc is formed by galvanic
displacement. This zinc deposit
effectively protects the surface from
re-oxidation and provides a sound basis
for subsequent electrodeposition. The
chemical processes involved may be
MacDermid Plc, Birmingham, UK
*tpearson@macdermid.com
DOI 10.1179/174591906X114516
summarised as
Al2 O3 z2NaOHz3H2 O?2NaAl(OH)4
3Na2 Zn(OH)4 z2Al(substrate) ?
2NaAl(OH)4 z4NaOHz3Zn(deposited)
The first reaction shows the reaction
for the dissolution of aluminium oxide
whereas the second illustrates the
galvanic displacement reaction.
Early forms of this preteatment
consisted simply of a solution of sodium
zincate. However, the level of adhesion
obtained by this type of process was
quite limited because the immersion
deposit of zinc tended to grow in an
uncontrolled manner and produce a
spongy deposit. Also, zinc itself is an
active metal and this limits the type of
plating process that can be applied.
In practice, cyanide copper
processes have to be used with these
so-called ‘simple zincate solutions’.
After the early zincate processes were
developed, it was quickly realised that
other metals in the zincate solution
could improve the properties of the
zincate immersion film. By adding
complexed iron to the process, the
immersion layer of zinc formed with a
much more tightly packed structure
and co-deposition of iron improved the
chemical resistance of the zincate
coating so that a wider range of plating
processes could be applied. Processes
were also developed incorporating
other metals into the process solution.
The most successful of these deposit
an alloy of zinc and copper. To limit the
rate of deposition of copper (which
would normally plate very quickly and
produce a powdery deposit),
complexed nickel is often used. These
types of solution often also contain a
small amount of cyanide, although
cyanide-free processes which work
well are now available.
Effectively, the zincate processes
that deposit a zinc–copper alloy tend to
produce a white brass alloy containing
about 15–20% copper by weight. This
coating produces high adhesion on a
Transactions of the Institute of Metal Finishing
wide range of aluminium alloys. The
relatively high percentage of copper in
the alloy also facilitates plating from a
wide range of plating solutions and
examples of metals that can be applied
directly to this type of coating include
copper, nickel, chromium, bronze and
tin. Zinc–copper alloy zincating
solutions have established themselves
as the most versatile processes for the
plating of aluminium.2–4
A wide range of aluminium alloys can
be processed by this method. Generally,
aluminium alloy components can be
split into two categories: castings and
extrusions, each of which have their
characteristic alloy compositions. To
obtain good flow properties during the
casting process, it is necessary to
include some silicon in the alloy.
Depending on the characteristics
required, casting alloys may contain up
to 14% silicon by weight. Extrusion
alloys are usually low in silicon, but often
contain magnesium, which is necessary
to provide precipitation hardening when
the alloys are heat treated. These
differences in composition mean that
different pretreatment cycles are
needed for the different types of
aluminium alloy.5
A typical process sequence for
casting alloys would be as follows:
N very mild alkaline cleaning to remove
greases from the surface of the
casting and prepare the surface for
the following stages. Usually, these
cleaners are silicate free because
silicates form a tenacious film on the
surface that can interfere with
subsequent process stages.
Ultrasonic agitation may be used to
increase the efficiency of the cleaner
N following degreasing, it is usual to
etch the castings using an alkaline
etchant. Aluminium castings are
polished mechanically before
plating, which tends to oxidise the
surface somewhat, and etching
effectively removes this oxide layer.
It is important to avoid over-etching
of the casting since this will open up
any underlying porosity
2006 VOL 84 NO 3 121
 NEWS AND VIEWS

N after alkaline etching, it is essential
that the components are rinsed
effectively. The next stage is often
referred to as ‘desmutting’. During
alkaline etching, the insoluble
components of the casting alloy
(silicon, iron, copper, etc.) are left on
the surface in the form of a black
‘smut’ which is loosely adherent
and, if not removed, will lead to poor
adhesion of the plated coatings. The
desmutting solution consists of a
mixture of nitric and hydrofluoric
acids and sometimes sulphuric acid.
A common composition is to use
50% nitric acid (70% grade), 5%
hydrofluoric acid (35% grade) or
ammonium bifluoride and 5%
sulphuric acid. This strong acid
mixture effectively removes smut
from the surface without
over-etching the aluminium (the
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Alkaline etching will not dissolve this
material and, since it etches the
aluminium, will enrich the magnesium
concentration at the surface. Because
of this problem, alkaline etching is best
avoided in the processing of extrusions.
Extrusion alloys are low in silicon so
fluoride containing desmutting
processes are also unnecessary and
may be counter-productive. A
double-dip sequence (which is optional
for casting alloys) is essential for the
processing of extrusions because of
their high hardness.
A typical process sequence for
extrusions would therefore be:
N as for castings, the first stage
consists of mild alkaline cleaning
which may be used in combination
with ultrasonic agitation to increase
its effectiveness
N
which may be applied mean that the
average ‘jobbing’ plater may have
difficulties in processing aluminium.
The following section offers advice for
successful processing of aluminium
alloys in the plating shop.
General advice for processing
of aluminium alloys
Know your alloy
All too often, components arrive for
processing with no hint of the alloy
composition or any heat treatment that
may have been given. Without this
knowledge, it is difficult to select an
appropriate pretreatment sequence.
There is no ‘universal’ pretreatment
sequence. Generally speaking, the
harder the alloy, the more difficult it will
be to process and the longer it will have
to be etched in the oxidising acid to

the parts are rinsed thoroughly then

nitric acid helps to passivate the remove the surface oxide layer. Alloys
treated in an oxidising acid dip
surface of the casting). Fluoride is up to T6 heat treatment can usually be
(usually a proprietary mix) to remove
necessary to remove silicon, which processed successfully but alloys of T7
surface oxidation and metallic smut.
it dissolves as silicofluoride and above may prove impossible.
The use of fluoride is unnecessary
Alloys that may be successfully
6HFzSi?H2 SiF6 z2H2 as the silicon content is low
electroplated are listed in Tables 1 and
Owing to the toxic nature of fluoride,
N the parts are then rinsed thoroughly
2. This is not a comprehensive list, but
and zincated using the double dip
an alternative process has been includes the most commonly
procedure described above for
developed that utilises ultrasonic processed alloys.
castings. Some alloys are unsuitable for
agitation to physically ‘shake off’ the
Following zincating, the components electroplating, e.g. castings that are too
silicon smut rather than dissolving it
are rinsed and then plated. Modern porous for processing or alloys having
chemically6
alloy zincate layers are quite chemically
N following desmutting, the
resistant and may be plated with a wide
an unsuitable composition. Common
unsuitable alloys are also listed in
component is again rinsed well to
range of topcoats using electrolytes Tables 1 and 2.
remove all traces of free acid from
including Watts nickel, electroless
the surface. The components are Know your process parameters
nickel, cyanide copper, pyrophosphate
then immersed in the zincate
copper and hard chromium. To process aluminium successfully, the
solution. Zincate processes usually
As can be inferred from the above, appropriate process must be selected,
operate at ambient temperature and
the wide diversity of alloys and coatings based on the alloy composition and
typical immersion times would be
60–90 s
Table 1 Cast alloys suitability for electroplating
N after zincating, the components are
rinsed again and are then ready for BS Designation Alloy type Suitability for plating
plating. However, the adhesion of
subsequent electrodeposits is often LM0 Al99.5 Excellent
LM2 AlSi10Cu2Fe Fair
improved using a ‘double dip’
LM4 AlSi5Cu3 Good
sequence. In this process, the initial LM5 AlMg5 Poor
zincate coating is removed by LM6 AlSi12 Fair
dissolving it in either 50% nitric acid LM9 AlSi12Mg Fair
or a proprietary oxidising acid dip. LM10 AlMg10 Unsuitable (Mg content too high)
The zincate coating is then LM12 AlCu10Si2Mg Fair
LM13 AlSi11MgCu Fair
re-applied. This second zincate
LM16 AlSi5Cu1Mg Fair
coating is thinner and more compact LM18 AlSi5 Fair
than the first coating and yields LM20 AlSi12CuFe Good
higher adhesion values than the LM21 AlSi6Cu4Zn Fair
single dip sequence (typically at LM22 AlSi5Cu3Mn Fair
least double the adhesion). LM24 AlSi8Cu3Fe Good
LM25 AlSi7Mg Fair
Extrusions are best processed using a LM26 AlSi9Cu3Mg Fair
slightly different sequence. During heat LM27 AlSi7Cu2 Fair
treatment, the magnesium added to LM28 AlSi19CuMgNi Unsuitable (castings often too
the alloy to increase hardening tends to porous for plating)
form a tenacious layer of magnesium LM29 AlSi23CuMgNi Unsuitable (see above)
LM30 AlSi17Cu4Mg Unsuitable (see above)
oxide on the surface of the extrusion.

122 Transactions of the Institute of Metal Finishing 2006 VOL 84 NO 3

 NEWS AND VIEWS

Table 2 Extrusion alloys suitability for electroplating Conclusions

Material designation (series) Suitability for plating The processing of aluminium alloys
depends upon many factors, including
1000 series: AlFe Excellent alloy composition, degree of heat
2000 series: AlCu3–5 Good
treatment and what metal is to be
3000 series Rarely used for general fabrications
4000 series Rarely used for general fabrications deposited as the first coating onto the
5000 series: AlMg3–5Mn Poor or unsuitable zincate layer. From a practical
6000 series: AlMg0.5–1 Good (up to T6 heat treatment) viewpoint, the important stages in
7000 series AlZn4–5Mg0.3 Unsuitable unless electrolytic zincate is applied aluminium processing are as follows:
N ensure the alloy composition and
heat treatment are known and that
level of heat treatment. If proprietary double dip sequence is mandatory if
the alloy is suitable for processing
processes are used, it is very good adhesion is to be obtained.
important that the manufacturer’s N select a suitable process sequence
Take care when plating the for the alloy, using a double dip
instructions are followed closely and
components sequence wherever possible
that the process baths are analysed and
maintained on a regular basis. Particular Zincated aluminium is delicate and is N ensure all the process parameters in
the pretreatment stage are within the
attention should be paid to the rinses subject to chemical attack by plating
manufacturer’s recommendations
on the pretreatment line since solutions. Because of this, it is
and that contamination is within
zincate coatings are prone to chemical recommended that the current is
acceptable limits
attack. The rinses following zincating applied to parts immediately on entry
should be clean and within a pH range into the plating solution. Never leave N ensure that the rinses are clean and
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within the required pH range

of 4–8.
Always use a double dip sequence
When production demands are high, it
is tempting to process aluminium using
a single dip sequence. However, on
many alloys, the adhesion obtained
with a single dip sequence is marginal.
Additionally, the first zincate layer is
always thicker than the second which
can compromise the corrosion
performance of the finished article:
when the coating is perforated, lateral
corrosion can occur at the zincate
interface.5 In most cases, when plating
castings, a double dip sequence will
give improved results. An exception to
this is very porous castings, where the
use of a second dip may give rise to an
unacceptable cosmetic appearance due
to etching of the aluminium surface. In
the case of extrusions, the use of a
zincated parts in the plating bath
without current. If the parts are to be
hard chromium plated directly, they
must be ‘struck’ at double the plating
current density for 30 s or so to obtain
good adhesion. Fluoride containing
chromium solutions are unsuitable for
processing aluminium alloys.
If the components are to be plated
with nickel from a Watts type
electrolyte, ensure the pH of the
solution does not fall below 4 and that
the temperature does not exceed 65oC.
If cyanide copper is used, a bath with
no ‘free’ sodium hydroxide must be
used to minimise chemical attack. If
copper pyrophosphate is used, ‘live’
loading at a low voltage is
recommended.
If all of the above factors are taken
into account, the processing of
aluminium should be straightforward.
N ensure that the plating solution is of
the appropriate type, pH and
temperature and that current is
immediately applied to the
components.
References
1. S. Wernick and R. Pinner: ‘The
surface treatment of aluminium
and its alloys’, Vol. 2, 4th edn;
1972, Stevenage, Finishing
Publications.
2. T. Pearson and S. Wake: Trans.
IMF, 1997, 75, (3), 93.
3. T. E. Such and A. E. Wyszynski:
Plating, 1965, 52, 1027.
4. A. E. Wyszynski: Trans. IMF, 1967,
45, 147.
5. J. W. Goby: PhD thesis, University
of Aston, Birmingham, 1981.
6. German Patent 300415, 1986.

Transactions of the Institute of Metal Finishing 2006 VOL 84 NO 3 123