Metal finishing with ionic liquids: scale-up and
pilot plants from IONMET consortium
E. L. Smith*, C. Fullarton, R. C. Harris, S. Saleem, A. P. Abbott and K. S. Ryder
The authors describe the successful
scale-up of five ionic liquid processes by
the IONMET consortium. Metal finishing
demonstrator technologies have been
developed based on ionic liquid systems
for the electropolishing of stainless
steels and other alloys, galvanic
immersion (dip coating) deposition of
silver for finishing of printed circuit
boards as well as electrolytic deposition
of hard chrome coatings, aluminium
coatings and barrel plating of Zn–Sn
alloys. It is shown that some of these
systems can be considered as ‘drop-in’
replacement technologies for existing
aqueous processes that currently require
strong inorganic acids and highly toxic
reagents.
Introduction
Commercial electroplating processes
based on aqueous technologies are
well established, but pressure is being
put on the metal plating industry to
reduce, or eliminate, the use of toxic
reagents such as cyanide or Cr(VI), in
compliance with environmental
legislation and together with increasing
process efÞciency to cut back on
energy usage.1 These have been the
driving forces behind the development
of so called ‘green technologies’. The
desire to deposit refractory metals
such as Ti and W and air/moisture
sensitive Al has driven research into
non-aqueous electrolytes. These
metals are abundant and excellent for
corrosion resistant coatings; however,
the stability of their oxides makes
these metals difÞcult to extract from
minerals and apply as surface coatings
from aqueous baths.2 Alloy deposits
that are difÞcult or impossible to
produce from aqueous electrolytes are
possible from ionic liquids (ILs).
Ionic liquids have emerged over the
last 15 years as alternative electrolytes
for electroÞnishing processes. The
Department of Chemistry, University of
Leicester, Leicester LE1 7RH, UK
*For correspondence: E.L.Smith@le.ac.uk
© 2010 Institute of Metal Finishing
Published by Maney on behalf of the Institute
DOI 10.1179/174591910X12856686485734
term ionic liquid has come to mean an
‘ionic material that is liquid below
100°C’.3 Ionic liquids have signiÞcant
properties that make them well suited
for metal processing electrochemistry:
wider potential windows than aqueous
systems, high solubility of metal salts,
high conductivity when compared to
other non-aqueous solvents and,
perhaps most importantly, unique
metal ion coordination chemistry.
Developing IL technology offers the
opportunity not only to electrodeposit
metals that have until now been
impossible to reduce in aqueous
solutions (because of limited potential
window or reactivity with water), but
also to design the redox chemistry of
the complex metal ion and thereby
control metal nucleation and growth
characteristics. Consequently the
electrolytic deposition of metals from
ILs has been the subject of an inten-
sive, sustained research effort and the
subject has recently been reviewed.4–8
Ionic liquids have been heralded for
many years as the Þrst viable alterna-
tives to aqueous solutions for metal
processing, but to date the large scale
adoption of this new technology has
not occurred due to the apparent
difÞculties with its application. In this
article, the authors aim to dispel some
of the perceived issues concerning
these liquids by summarising the
outcomes of an EU funded project,
IONMET,9 founded to develop IL
processes for industrial use.
Outline of IONMET project
‘New Ionic Liquid Solvent Technology
to Transform Metal Finishing Products
and Processes’ is the title of a
57-month integrated FP6 EU project
consisting of 33 partners, mainly SMEs,
but also higher education, research
institutions, trade associations and
large industrial companies (see
Appendix). The overall objective
of the project was to introduce
breakthrough IL technology with the
potential to transform the scope and
competitiveness of industrial metal
Þnishing processes. The project was
Transactions of the Institute of Metal Finishing
focused mainly on the exploitation of
choline chloride based binary ILs also
known as deep eutectic solvents,
however, for reactive metals such as Al,
imidazolium systems were developed.
In this article the scale-up of Þve
room temperature IL metal deposition
processes are described. Metal
Þnishing demonstrator technologies
have been developed based on IL
systems for the electropolishing of
stainless steels and other alloys,
galvanic immersion (dip coating)
deposition of silver for Þnishing of
printed circuit boards as well as
electrolytic deposition of hard chrome
coatings, aluminium coatings and
barrel plating of Zn–Sn alloys.
Demonstrator units
Generally, the processes detailed
below can be described as having low
environmental impact/toxicity, are
inexpensive and easy to handle. It is
shown that some of these systems can
be considered as ‘drop-in’ replacement
technologies for existing aqueous
processes that currently utilise strong
inorganic acids and highly toxic
reagents. Many of the ILs described
here are composed of binary eutectics,
also known as deep eutectic solvents.
Deposits have been characterised
using a combination of scanning
electron microscopy, atomic force
microscopy, acoustic impedance
spectroscopy, X-ray techniques and a
range of DC and AC electrochemical
methods. Unfortunately, due to short
time scales at the end of the IONMET
project some of the characterisation
that the consortium would have liked to
perform on pieces from the scaled-up
demonstrator units, such as bend tests
for adhesion assessment, were not
possible.
Electropolishing
The IONMET consortium has success-
fully built and operated a pilot scale unit
for electropolishing of 300 series
stainless steels and other nickel
containing alloys (Fig. 1). This unit was
2010 VOL 88 NO 6 285
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1 Electropolishing pilot plant in use,
showing cascade rinse tanks
designed and constructed using
established technologies and materials
such that the only substantive differ-
ence is the electropolishing electrolyte,
i.e. a drop-in replacement. The pilot line
has aqueous degrease, cascade rinse,
mild aqueous pickle, cascade rinse
followed by the IL process tank and a
Þnal set of two cascade rinse tanks.
The process volume for IL electrolyte is
around 60 L. Lip extraction is built into
the degreasing, pickle and process
tanks and polypropylene was used for
all tank construction. The control unit
contains a low ripple rectiÞer, which
can be operated under voltage or
current control. Dual temperature and
2 Optical micrographs of a unpolished area and b polished area of sheet of 316
stainlesss steel; three-dimensional plots of atomic force microscopy images of
c unpolished region and d polished region of stainless steel
286 Transactions of the Institute of Metal Finishing
level controls are also built in as well as
air spargers on all tanks.
A range of stainless steel samples
have been trialled (in collaboration with
IONMET partner and specialist
electropolishers, Anopol10) including
small pressed/folded plates, cast pipe
Þttings, pipe lengths of different
diameters, wires and Þne mesh. A high
degree of success and consistency has
been obtained on many of these
components giving mirror bright
Þnishes, with surface roughness and
etch rate data comparable or even
better than the established phosphoric/
sulphuric acid based electrolyte. The
results of surface characterisation of a
stainless steel sheet before and after
electropolishing in the IL bath can be
seen in Fig. 2. Specialist jigging is
occasionally required for components
of complex shapes but this is no
different to the established methods.
The liquid consists of a 2:1 stoichio-
metric mixture of ethylene glycol and
choline chloride; some of the funda-
mental electrochemistry and surface
science has already been described in
detail.2,11,12 In addition to this, however,
there are proprietary additives that are
crucial to the Þnish; these need to be
monitored and adjusted as a function of
usage in order to maintain process
control. The process is typically
operated at around 40–50°C under
voltage control at ∼6.0 V using
dimensionally stable cathode mesh.
The current efÞciency of the IL process
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is ∼80%, which is much better than the
aqueous acid electrolyte because of
the lower H+ ion activity. Hydrogen gas
evolution is also much lower as a
consequence. The handling environ-
ment is much improved over the
aqueous acids in that the vapour
pressure is very low; the liquid has
very low toxicity and is essentially
non-corrosive by comparison. Recycling
protocols for isolation of dissolved
metals in spent electrolytes have been
developed and described recently.13 In
addition, the authors will shortly publish
here details of life cycle studies and
comparative longevity data for the IL
electrolyte against the aqueous acid
systems. A photograph of a standard
stainless steel tube testpiece electrop-
olished in the demonstrator unit can be
seen in Fig. 3.
3 Stainless steel tube of 25 mm diam-
eter that has been masked and
polished (top) in IL tank: difference
in optical brightness to unpolished
region (bottom) is clearly visible
In addition to good performance of
the pilot scale unit in stainless steel
trials, the authors have also studied
other alloy systems, particularly those
nickel based systems associated with
high value/performance components
for challenging mechanical and thermal
environments. Nickel based alloys are
very difÞcult to electropolish using
aqueous electrolytes because of rapid
pitting and anisotropic dissolution rates.
This is not the case in the choline
chloride IL system and Ni–Co alloys
together with a range of aerospace
superalloy systems polish very well.
This market is clearly a strategic focus
for commercialisation since the high
value of such Þnished components
makes economic investment and
associated risk in new technology more
acceptable, especially when that same
technology offers other convincing
attributes such as unique process/
functionality improvements as well as
unequivocal environmental beneÞts.
This pilot unit is situated at the
University of Leicester Ionic Liquids
Demonstrator facility, which is

dedicated to interacting with industry in
such a way as to jointly address
practical issues and problems as well
as push out new IL technology.14
Hard chromium electroplating
Cr(III)-containing ILs could be a suitable
alternative to hexavalent chromium
baths for the deposition of hard
chromium coatings. A new chromium
plating bath has been developed using
a system based on choline chloride and
the less toxic source of chromium,
CrCl3.6H2O.7,15,16 The bath does not
contain acid or CrO3, the formulation is
simple to make and tolerates some
water. Negligible gas evolution is
observed during plating. The absence
of hydrogen production during plating
will eliminate the potential for hydrogen
embrittlement, a signiÞcant factor for
component failure.
Figure 4 shows the demonstrator in
situ at the University of Leicester. The
pilot plant consists of an aqueous
H2SO4 anodic etch tank, a water rinse,
the IL plating tank and a Þnal water
rinse tank. The unit has built-in
continuous process monitoring;
coulometry and conductivity data are
recorded in the main tank. A separate
Cr3+ reservoir and dosing pump
facilitates automatic maintenance of
the bath composition as a function of
total charge passed (i.e. metal plated
out), while the conductivity of the bath
is used to monitor water content. This
unit was designed and built by IONMET
partner C-Tech Innovation17 with some
of the preliminary laboratory trials being
carried out at both the University of
Leicester and Association pour la
Recherche et le Développement des
Méthodes et Processus Industriels,
France.
Plating conditions have been
optimised for Cu and mild steel
cylindrical testpieces (dia. 25 mm,
length 40 mm). Deposits are generally
made at a constant current density of
4 Hard chromium demonstration unit
built by C-Tech and installed at Uni-
versity of Leicester
0.6 A cm−2 for between 45 min and 1 h.
The physical properties of the IL
change markedly with temperature and
composition, and above 65–70°C the
5 Cylindrical Cu testpieces that have
been plated using hard chromium
demonstrator: bottom cylinder has
been mechanically buffed after
plating; top cylinder has experi-
enced no further processing after
removal from plating bath
colour of the liquid changes to purple
showing that the coordination sphere
around the chromium centre is
changing. The temperature in the
demonstrator unit is maintained at
40°C by using a cold water cooling coil.
There are three main aqueous hard
chromium plating baths currently in
operation in industry: a sulphate only
containing bath known as Sargeant
solution, a ßuoride catalysed sulphate
process and an organic acid salt/
sulphate process. The corrosion
resistance, current efÞciency and
hardness of deposits vary with bath
composition and some of these can be
found summarised in Table 1 and
compared with the current values for
the IL process. The hardness of the
deposit from the IL bath can be
increased to ∼1100 HV by further heat
treating. The current efÞciency for the
IL process can be as high as 90%
(black chromium); for hard chrome it
depends on the formulation of the bath
but is in the region of ∼40%. Hard
Table 1 Comparison of hardness and current efÞciency for three main aqueous
hexavalent hard chromium processes and trivalent hard chromium IL bath*
Deposit hardness/HV
Hard Cr(VI) baths
Sulphate only (Sargeant) 800–1000
Fluoride/sulphate 950–1050
Acid/sulphate 1000–1200
Hard Cr(III) baths
Ionic liquid 600–700
*Data for the aqueous hexavalent chrome processes taken from ‘Chromium Plating’
by Chrissy Bieler, PF Online, Gardner Publications Inc.
Transactions of the Institute of Metal Finishing
BULLETIN
chromium plating based on aqueous
chromic acid results in an inherently
inefÞcient process; only 10−20% of
the energy supplied is claimed to be
utilised for electrodeposition.18 Modern
high efÞciency baths can reach ~25%
(Table 1). Also, the deposition of the
metal from CrVI naturally necessitates
twice as much charge as the corre-
sponding Cr(III) complex.
The amount of microcracking found
in the resultant chromium deposit
depends greatly on the experimental
conditions under which the chromium
was plated, i.e. whether a high current
density was used for a short time scale
or vice versa. Hard chromium pieces
are often Þnished by precision grinding
in order to produce a level, smooth
surface; this requires adhesion to be
good. Adherence of the chromium layer
from the IL is still being optimised,
however, as can be seen in Fig. 5, the
50 μm chromium layer is sufÞciently
adherent to allow mechanical bufÞng.
Anode reactions
The authors have operated the current
chromium plating processes using
either dimensionally stable anode (DSA)
(Pt/Ir oxide coated Ti) mesh or soluble
chromium metal. The DSA mesh
results in chlorine gas evolution at the
anode and this accounts for a large
proportion of the anode current. It was
for this reason that the pilot unit was
situated in a purpose-built walk-in fume
hood (Fig. 4). When used with soluble
chromium no chlorine gas was
detected; good coatings were obtained
by each method. In using a soluble
chromium source there is always some
concern over the oxidation state of the
dissolved species, but no evidence has
been seen to suggest that any
hexavalent chromium is produced
during dissolution at the anode.
Nevertheless, concerns remain about
the economic feasibility of soluble
chromium anodes and, on a more
practical level, there are also variations
Current efficiency/%
10–13
22–25
23–26
∼40
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BULLETIN
6 Mild steel (left) and copper (right)
rod coated with Al from imidazolium
based plating bath
in throwing power. Overall current
efÞciency was shown to vary with
anode material and also was strongly
dependent on the composition of the IL
electrolyte. Values ranging from 40%
up to 80% were determined. In the
case of the lower efÞciency values the
pathways of lost current density are
mostly known and well deÞned but are
subject to proprietary information
relating to composition and so cannot
be detailed here.
Aluminium plating
During the IONMET project there
emerged a strategic requirement
among the many SME partners for an
aluminium plating process as an
alternative to the costly and hazardous
process involving pyrophoric AlEt3. The
application areas for such coatings
focused on anticorrosion coatings for a
wide variety of technologies but with a
special focus on aerospace as an
alternative to cadmium. This is part of a
general theme developed here; also in
this article the authors describe Zn–Sn
coatings from ILs that were formulated
as alternatives for the same purpose. In
addition, there were some aesthetic
applications for Al coatings on a variety
of substrates.
The authors have, as a consequence,
developed a process for Al plating that
is effective and gives coatings of even
and uniform morphology over a variety
of testpieces on mild steel and copper
substrates. Surface Þnish can be
controlled and can be either white matt,
black or mirror bright depending on the
liquid formulation and current density.
Testpiece geometries typically included
cylindrical rods (about 5×150 mm) or
larger scale ßat plate pieces
(20×20 cm). Coating thicknesses of up
to 200 μm were achieved opening up
the possibility of electrochemical
micromachining applications. Adhesion
is good on Cu substrates or Cu coated
288 Transactions of the Institute of Metal Finishing
mild steel (see Fig. 6). Adhesion of
coatings directly onto steel is a strong
function of steel composition and
pretreatment regime. The measure-
ment of, and inßuence of surface
stress on, adhesion during deposition
will be published later, in detail.
The liquid used in this process is an
imidazolium based chloroaluminate
system, which is in itself not a new
concept. Indeed, such systems were
among the Þrst ILs investigated.19 How-
ever, embodied in this process is some
new understanding and insight into the
role of certain diluents and additives
that are crucial to the performance of
the electrolyte in the process.20,21 Also
important are the anode reactions and
the anode geometries. Typically soluble
Al anodes were used in most testing
and current efÞciency measured by
both bulk mass difference and
microgravimetric determination using
quartz crystal microbalance techniques22
was essentially quantitative. Effects of
current density and potential for
nucleation and deposition from this and
similar liquid formulations were
recently discussed in detail alongside
comparisons of aged and regenerated
liquids as an insight into process
issues for extended lifetime of the
electrolyte.20,21
The small pilot plant is shown in Fig. 7.
This consists of a nitrogen gas
containment purge box constructed
from stainless steel coated with
corrosion resistant polymer on the
inside with three built-in process tanks
and a fast entry evacuateable port for
sample exchange. The tank process
materials are polypropylene and
polyvinylidene ßuoride (PVDF). The
tanks consist of a rinse/degrease step,
a plating process tank with tempera-
ture control set around 50°C and
circulation, and a Þnal rinse/passivation
tank. The main process tank contains
7 Al plating prototype in use shortly
after commissioning: sample access
is good via evacuateable fast entry
port (right)
2010 VOL 88 NO 6
∼70 L of IL electrolyte heated with
polytetraßuoroethylene (PTFE)
elements and controlled with PTFE
shielded thermocouples. The built in
rectiÞer can be operated in constant
current or potential mode and is
equipped with polarity reverse to
facilitate in situ etching. This unit was
designed and built by IONMET partner
C-Tech Innovation.17
In many respects the use of
imadazole based electrolytes is only
an interim solution to the Al problem
because the cost of the imidazolium
cation is still very high and likely to
remain that way. On the other hand,
this process is reliable and much safer
than the only alternative even with the
use of organic solvents as diluents,
additives or for pre- or post-processing.
The IONMET consortium has shown
that this system can be operated at the
70–100 L scale and that it represents a
viable process. Economic constraints
may limit all similar processes to high
value niche applications such as
aerospace, e.g. in areas including
functional barrier coatings, anticorro-
sion and aesthetics, and this is where
commercial exploitation is, at least in
the Þrst instance, most likely.
However, in further recent work at
the University of Leicester another
formulation has been developed for a
chloroaluminate based IL that is based
on much simpler and less expensive
components. Good quality coatings
of Al have been produced from this
new electrolyte although less is known
about the molecular electrochemistry.
This process is currently under patent
review and details will be published
shortly.
Immersion silver
An IL immersion silver process was
developed as an alternative protective
surface for electronic components to
aid solderability.23–25 The existing acid
based aqueous process for Ag coating
of printed circuit boards (PCBs)
contains toxic and corrosive chemicals
which degrade copper tracks (solder
mask interface attack). In order for the
IL process to compete with existing
aqueous technology the silver must be
of a suitable thickness, aesthetically
pleasing, have a good shelf life,
produce a reliable solderable Þnish and
be cost effective (an example of a PCB
coated using the IL technology can be

8 a example of PCB Þnished with immersion Ag from IL demonstration line and b SEM image of solder joint showing good
intermetallic
seen in Fig. 8). The liquids themselves
are in principle economically competi-
tive with the aqueous process due
primarily to the simplicity (and compa-
rable cost) of the silver salts used and
the lack of precious metal catalyst.
The sustained deposition of metallic
silver is obtained from an IL based
on choline chloride and ethylene glycol
without the need for a precious metal
catalyst or complex surface prepara-
tion. It is important to note that the
process described here is an immer-
sion displacement process. As a result
copper is dissolved as silver is depos-
ited (in a 1:1 mole ratio). The beneÞt of
this process compared to that of
competitive etching in nitric acid based
baths is that copper is only displaced
from regions where silver is plated,
whereas acid etching is indiscriminate
and unselective, which can lead to
open circuit failures.
The deposition rates were investi-
gated by quartz crystal microbalance
techniques which have been described
in detail before.23 The rate of silver
deposition is quite sensitive to
temperature and silver salt concentra-
tion, and thickness can be effectively
controlled by immersion time. For
example the deposition rate can be
increased from 45 to 110 nm min−1 by
increasing the temperature from 20 to
45°C. The concentration of the silver
salt does not appreciably affect the
surface roughness. A deposition rate of
∼0.2 μm min−1 is achieved which is
viable for a commercial immersion
deposition process and corresponds to
an immersion time of ∼2 min to deposit
0.5 μm of silver.
Scanning electron microscopy and
atomic force microscopy investigations
revealed no solder mask interface
attack from the solution. Solder mask
interface attack occurs when the
aqueous acidic solution attacks the
solder mask; if copper is removed from
underneath the edge of the solder
mask, ßakes of mask lose adhesion.
The sustained growth of silver is
facilitated by the pores and channels
within the deposit through which ionic
species can move.
The silver deposited from the IL
dissolves in the solder joint at a lower
soldering temperature compared to
that from aqueous systems, giving a
good solder to copper intermetallic (see
Fig. 8) and improved surface wetting.
The solderability has been assessed by
external test facility ITRI using standard
wetting balance methods. A selection
of British Standard test coupons were
manufactured, brushed and processed
through the above IL silver immersion
line, then hand assembled and
soldered. Solderability testing and
accelerated aging tests were per-
formed on small PCB tokens and fully
fabricated multilayered PCB testpieces
using industry standard methods.
The process has been scaled up to a
prototype facility for demonstration
purposes, currently housed at PW
Circuits (Wigston)26 (see Fig. 9). The
prototype incorporates twelve 140 L
process tanks consisting of ∼800 L of
IL within Þve IL etching, rinsing, or
deposition tanks. It has the capacity to
Ag coat full size multilayer PCBs. The
plant uses conventional construction
materials (polypropylene tanks and
Þttings) and methods; and is arranged
as a series of temperature controlled
tanks with a basic lip extraction for
each tank and an oscillating ladder rack
for the agitation of the PCB jigs during
deposition in order to facilitate coating
of the inside of drilled interconnecting
holes.
Zn–Sn barrel plating line
Zn–Sn alloys have been deposited from
a variety of aqueous baths and have
Transactions of the Institute of Metal Finishing
BULLETIN
been found to have better corrosion
resistance than pure zinc, particularly in
high humidity conditions. A full range of
alloys cannot be deposited from
aqueous solution; they are limited to a
deposit with a maximum of 30%Zn
content. Ionic liquids present a radically
new cost effective technology for
tuning the alloy compositions of
protective coatings. A range of Zn
alloys (with Cu, Fe, Ni and Sn) have
been successfully deposited from ILs
and the systems characterised.
In the IL process, it is possible to
tune the composition of the alloy
across almost the full range by
adjusting the bath composition and
process conditions, such as current
density, temperature and metal
concentration.27 Deposit morphology
changes with current density, hydrogen
bond donor and solution composition.
Corrosion testing (salt spray) has
shown some Zn–Sn coatings are better
than comparable aqueous formed
coatings.
The Zn–Sn alloy deposition process
has been developed in laboratory scale
trials by Protection des Métaux
(France)28 and Fundacion Inasmet
(Spain)29 and has then been scaled up
by JMP Ingenerios (Spain) and
Fundacion Inasmet. In order to prove
the suitability of IL technology in a
production barrel plating line a demon-
strator has been constructed to deposit
a protective surface coating on a
standard steel bolt of 561 mm2 surface
area, with an initial load of 100 bolts in
the initial trials. The prototype consists
of 16 tanks distributed in two parallel
lines and can be fully automated using
control software (see Fig. 10). The 16
tanks include aqueous pre and post-
plating treatment steps, with an IL
plating tank. The IL plating bath in the
prototype has been optimised to
deposit an alloy coating with an
2010 VOL 88 NO 6 289
BULLETIN
9 Ag demonstration line in situ at PW Circuits Ltd (Wigston)
approximate composition of 25%–75%.
The IL plating bath consists of a 2:1
stoichiometric mixture of ethylene
glycol and choline chloride, ZnCl2 and
SnCl2 and some proprietary additives.
The coatings are deposited at 55°C at
1.8 V. The Zn–Sn coatings were
passivated with common aqueous
commercial methods and in general
the new passivated coatings showed
good performance in salt spray fog
corrosion testing.
Alongside this work, Protection des
Métaux has successfully developed a
Zn–Sn alloy coating that contains
∼70%Zn for speciÞc use in the
aerospace industry as a replacement
process for Cd deposition (see Fig. 11).
It would not be possible to achieve this
high Zn containing alloy from current
aqueous systems. This particular bath
formulation for high Zn content alloys
has not been incorporated into a
demonstrator unit at present.
11 Photograph of pieces coated with
Zn–Sn alloy that contained ∼70%Zn,
developed by Protection des Mé-
taux
General comments
Material compatibility is an important
issue when designing a plant for use
with ILs. The liquids themselves are
290 Transactions of the Institute of Metal Finishing
10 Barrel plating prototype line in situ at Fundacion Inasmet
(Spain)
generally stable with most polymers
such as polyethylene, polypropylene,
nylon, Teßon, PVDF and polyvinyl
chloride (PVC). The addition of an
oxidising agent such as silver (Ag(I))
decreases the compatibility with
elastomers but in most cases heavily
ßuorinated elastomers are suitable. The
main material incompatibilities are with
metals. Consequently all internal
Þxings, e.g. nylon or Ti screws, PTFE
shielded temperature probes, were
carefully chosen and non metallic pump
rotors and pipe work were used in
construction of the demonstrator units.
During the IONMET project it has
become apparent that ethylene glycol
has some environmental issues that
may limit process use for some
markets, particularly in the USA.
Consequently, the authors have set
out to evaluate the performance of
substitutes in the liquid formulation
for immersion silver plating and other
applications. Propylene glycol has been
considered as a stoichiometric
substitute as it has no restrictions on
its use and may be more suitable in the
long term. It is, however, considerably
more expensive which will affect the
overall economics of the process. The
results were very positive; while these
tests are not by any means exhaustive
the results suggest that propylene
glycol can be a substitute in the
formulation of the liquid where
ethylene glycol can no longer be used
without loss of functionality or
application.
Conclusions
In this paper the authors have described
the electrolytic and immersion
2010 VOL 88 NO 6
deposition of a range of metallic
coatings and alloys from room tem-
perature ILs including chloroaluminate
melts and deep eutectic solvents based
on choline chloride. In particular, the
latter have low environmental impact/
toxicity, are inexpensive and easy to
handle, thereby fulÞlling many of the
requirements for so called green
technologies. Prototype units have
been developed to show that immer-
sion silver plating of PCBs and
electropolishing of stainless steels and
Ni–Co alloys, can be considered as
drop-in replacement technologies for
existing aqueous processes based on
strong inorganic acids and highly toxic
reagents. In addition, it has been
shown that through the IONMET
consortium the authors have been able
to bring several other key processes to
scale-up and precommercialisation
trials. These include: Al plating, hard Cr
plating, and Zn–Sn alloy plating. During
the early beginnings of IL technology it
was mainly only university start-up
companies that were investigating ILs,
now the high potential of these
systems has motivated large compa-
nies such as Merck and BASF to
become involved in the development of
specialised systems.30 In fact the
potential of ILs for Al deposition has
already been recognised by both the
Sigal and the Philips processes.31, 32
With this in mind the development of a
large-scale surface Þnishing process
utilising ILs looks promising.
Acknowledgement
The IONMET consortium would like to
express gratitude for funding through
the EU Framework Programme 6.

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Transactions of the Institute of Metal Finishing
BULLETIN
Appendix
The IONMET project consists of 33
European partners. The consortium
consists of highly ranked R&D provid-
ers and leading European SMEs in
plating and printed circuit technology:
1. Genacys Limited, UK (Coordinator)
2. Galvotech Limited, Ireland
3. Lacaze S.A., France
4. T&S Sistemi S.a.s., Italy
5. Fundacion Inasmet, Spain
6. Instytut Metali Niezelaznych, Poland
7. Deutsche Gesellschaft für Galvano
und rßächentechnik e.V., Germany
8. C-Tech Innovation Ltd, UK
9. Faculdade de Ciências da Universi-
dade do Porto, Portugal
10.Anopol Limited, UK
11.CEA – Commissariat a L’Energie
Atomique, France
12.University of Leicester, UK
13.PW Circuits Limited, UK
14.Inter Euro Technology Ltd, Ireland
15.Groupe Mecachrome, France
16.Poeton Limited, UK
17.University of Clausthal, Germany
18.Rohm and Haas, Electronic
Materials Deutschland GmbH,
Germany
19.Ashton & Moore Limited, UK
20.Centre Technique des Industries
Mécanique, France
21.Institut für Materialprüfung und
Werkstofftechnik GmbH, Germany
22.Protection des Métaux, France
23.Association pour la Recherche et le
Développement des Méthodes et
Processus Industriels, France
24.European Institute of Printed
Circuits, The Netherlands
25.MEP Applications BVBA, Belgium
26.KaHo - Katholieke Hogeschool Sint-
Lieven, Belgium
27.Galvanotecnia y Derivados S.A.,
Spain
28.AKABA, Spain
29.Specialised Metals, Ireland
30.Franz Oberßächentechnik GmbH,
Germany
31.Derost s.r.o., Czech. Rep.
32.SITA Aerospace, France
33.JMP Ingenerios, Spain
2010 VOL 88 NO 6 291
 Contents
Volume 88 2010
6 Aerospace engineering coatings: today and next 5 years
G. Armstrong
8 Contribution of nanomaterials to high corrosion protection
D. Labouche and B. Parrott
11 Platinum plating for turbine blades: technology development and process improvement
S. J. Hemsley and W. Zhou
16 Meeting report: Institute represented in European debate
P. Wynn
17 Use of platinised titanium anodes in chrome plating applications in aircraft industry
J. Wurm and P. Morrell
21 Hard anodising of aerospace aluminium alloys
L. M. Lerner
24 Conference report: Eurofinish 2009
A. Cobley
28 Nano-electrodeposition for hard magnetic layers
P. L. Cavallotti, M. Bestetti, S. Franz and A. Vicenzo
35 Effect of elastic compliance of PYSZ EBPVD thermal barrier coatings on cyclic test lives
B. Williams
41 Fluoride treatment and sol film composite technology for AZ91D magnesium alloy
J. Y. Hu, Q. Li, X. K. Zhong and F. Luo
47 Nanostructured Co–W coatings produced by electrodeposition to replace hard Cr on aerospace components
D. P. Weston, S. J. Harris, H. Capel, N. Ahmed, P. H. Shipway and J. M. Yellup
57 Anodic oxidation and sol–gel coatings for corrosion and wear protection of AM60B alloy
M. Bestetti, A. Da Forno, P. L. Cavallotti, P. Gronchi and F. Barlassina
70 Advantages of biochemical technology applied to paint detackification
P. Wynn, C. Virion and J. Kochilla
75 Successful cyanide free plating protocols on magnesium alloys
X. P. Lei, G. Yu, Y. P. Zhu, Z. P. Zhang, X. M. He, B. N. Hu and Y. Chen
81 Symposium report: Whiskers
G. D. Wilcox
83 William Blum – grand old man of American electroplating
D. R. Gabe
84 Copper deposition at segmented, reticulated vitreous carbon cathode in Hull cell
R. C. Tangirala, C. T. J. Low, C. Ponce-de-León, S. A. Campbell and F. C. Walsh
93 Study of corrosion resistance and nanostructure for tertiary Al2O3/Y2O3/CNT pulsed electrodeposited Ni based nanocomposite
S. Mirzamohammadi, R. Kiarasi, M. K. Aliov, A. R. Sabur and A. Hassanzadeh-Tabrizi
100 Electrodeposition of chromium–cobalt alloy from Cr(III) formate-urea electrolyte
S. Survilienė, A. Češūnienė, A. Selskis and R. Juškėnas
107 Conversion coatings for zinc electrodeposits from modified molybdate solutions
O. D. Lewis, D. Greenfield, R. Akid, R. H. Dahm and G. D. Wilcox
120 Symposium report: Targeted testing for cost reduction
C. Larson
122 Electroplating with non-aqueous solutions
L. Brown
124 REACH – mounting concerns for the surface finishing industry
P. A. W. Lansdell
129 Roy Hammond: defence finishing researcher
D. R. Gabe
130 Au electrodeposition in presence of self-assembling organics: in situ study by sum frequency generation and surface enhanced Raman
spectroscopy
B. Bozzini, L. D’Urzo, C. Mele, B. Busson and A. Tadjeddine
144 Role of SPS in chloride ions and PEG additive system for copper electrocrystallisation
M. Gu, Q. Li, B.-H. Fu and X.-H. Xian
149 Effect of PEG molecular weight on bottom-up filling of copper electrodeposition for PCB interconnects
L. Yin, Z. H. Liu, Z. P. Yang, Z. L. Wang and S. Shingubara
154 Analysis of thin impurity doped layers in anodic alumina and anodic tantala films by glow discharge time-of-flight mass spectrometry
I. S. Molchan, G. E. Thompson, P. Skeldon, N. Trigoulet, A. Tempez and P. Chapon
158 Comparison of sliding wear behaviour of pulse electrodeposited Ni–Cu nanocrystalline alloys and Ni–Cu/Cu multilayers
S. K. Ghosh, P. K. Limaye, C. Srivastava and R. Tewari
163 Ecologically green conversion coating for zinc–cobalt alloy
G. Bikulčius, A. Ručinskienė, A. Selskis and A. Sudavičius

292 Transactions of the Institute of Metal Finishing 2010 VOL 88 NO 6

 BULLETIN

166 Cavitation intensity of solutions of chemicals used as components of media for ultrasonic cleaning in aqueous alkaline solutions
B. Niemczewski
174 Letter to the Editor
C. Barnes
174 Obituary – Don Haynes
175 Seminar report: IONMET and SurfEnergy
C. Larson
177 Seminar report: Pulse plating development continues to mature
J. P.G. Farr
178 Roberto Piontelli: ‘Grand seigneur’ of electrochemical science
P. L. Cavallotti
179 Engineered coatings for composites and polymers used in defence and aerospace: now and the future
G. Armstrong
185 CFD analysis of eductor agitation in electroplating tank
L. Z. Tong, K. Ohara, F. Asa and Y. Sugiura
191 Nickel electrodeposition from novel lactate bath
M. M. Kamel, Z. M. Anwer, I. T. Abdel-Salam and I. S. Ibrahim
198 Electroless silver deposition on ABS plastic using Co(II) as reducing agent
M. Selvam
204 Effect of intensities of ultrasound sonication on reduction of crack formation and surface roughness in iridium electrodeposits
T. Ohsaka, Y. Goto, K. Sakamoto, M. Isaka, S. Imabayashi and K. Hirano
209 Characterisation of mechanical properties of electrochemically deposited thin silver layers
S. Cherneva, R. Iankov and D. Stoychev
215 Electroless deposition of copper from methane sulphonate complexed bath
S. Rekha, K. N. Srinivasan and S. John
220 Effects of alkaline cleaners and cleaning methods on phosphate coating weight and surface morphology
S.-L. Zhang, X.-L. Zhang, M.-M. Zhang, Q. Ma and W.-W. Li
225 Obituary – Dr Sheelagh Campbell FIMF
231 President’s “End of term” report
R. S. Briggs
232 Workshop Report – Surface analysis for metal finishing
A. Cobley
234 Operating map – a tool for plating functional layers
W. Paatsch and G. Mollath
237 Review: Recent advances in pulsed current electrodeposition: a brief review
C. Larson and J. P. G. Farr
243 Pulse and pulse reverse plating of copper from acid sulphate solutions
P. Leisner, M. Fredenberg and I. Belov
248 Pulse plating of matt tin: effect on properties
A. Vicenzo, S. Bonelli and P. L. Cavallotti
256 Corrosion properties of double layer nickel coatings obtained by pulse plating techniques
N. Imaz, E. Garcia-Lecina and J. A. Diaz
262 Electroplating, electrode kinetics and electrocrystallisation
J. P. G. Farr
266 Periodic reverse current electrodeposited nickel pigmented anodised aluminium
M. Zemanova, P. Krivdova and J. Valtyni
272 Influence of additives and pulse parameters on uniformity of through-hole copper plating
Z. X. Wang, S. Wang, Z. Yang and Z. L. Wang
277 Hydrogen embrittlement in electroplating: avoidance using pulse plating
W. Paatsch
281 Symposium-Future technologies, applications and opportunities for surface engineering
G. D. Wilcox
284 Svante Arrhenius
D. R. Gabe
285 Metal finishing with ionic liquids: scale-up and pilot plants from the IONMET consortium
E. L. Smith, C. Fullarton, R. Harris, S. Saleem, A. P. Abbott and K. S. Ryder
294 Numerical analysis of film thickness of electrodeposited paint coating for whole automotive body using virtual surface
K. Ohara, L. Tong, K. Sakita and Y. Hayashi
303 Fatigue and fracture assessment of replacements for toxic metal coatings for aerospace applications
A. M. Cree, M. Devlin, G. Critchlow and T. Hirst
311 Electrochemical behaviour of high phosphorus electroless Ni-P-Si3N4 composite coatings
J. N. Balaraju, V. Ezhil Selvi and K. S. Rajam
317 Electrodeposition of high performance multilayer coatings of Zn-Co using triangular current pulses
S. Yogesha and A. C. Hegde
324 Study on corrosion behaviour of nanocrystalline and amorphous Co-P electrodeposits
M. A. Sheikholeslam, K. Raeissi and M. H. Enayati
330 Annual Indexes

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