An Overview of Hard Chromium Plating Using Trivalent Chromium

Solutions.
Patrick BENABEN,
Profesor, Ecole Nationale Superieure des Mines de Saint-Etienne
880 avenue de Mimet 13540 Gardanne France
benaben@emse.fr


Abstract
For more than forty years, academic and industrial researchers from all around the world have
taken a strong interest in alternative processes for hard chromium plating using hexavalent
ions.
Substitution processes benefits are obvious, as the toxic and carcinogenic aspects of
hexavalent chromium are well known. A tremendous energy has been spent on researching
processes using dry research technology (HVOF, PVD-CVD, thermal treatment,), as well as
wet technology, such as electrodeposition or electroless deposition of metals or composite
(Nickel or Cobalt with or w/o particles). Currently HVOF and Ni electroless (particles)
processes seem to be the most promising solutions. However some drawbacks (NLOS
surfaces, hardness, friction coefficient, corrosion or wear resistance, adhesion) bother the
development of these methods and their establishment as the universal solution.
The use of trivalent chromium as theion for chromium plating seems to be intrinsically the
most interesting mode to obtain hard deposits, approximately in the same conditions and
characteristics as for hexavalent mode. There have been a lot of attempts over the past
decades to use trivalent chromium ions in different chemical compositions of aqueous
solution, ionic liquids and different current waveforms however not meeting the expected
results.
The objective of this presentation is to describe, on an historical and technical level, these
different attempts, which have been made in the past. General characteristics, results,
advantages and drawbacks of the different processes will be described from the first tries, to
the very most recent development.






I General aspects :

Chromium electrodeposition is generally achieved by electrochemical reduction of hexavalent
solutions containing catalysts such as sulfate, fluosilicic ions or proprietary catalysts at a
temperature of about 50 to 60C and a cathodic current density between 10 to 60 A/dm.
These hexavalent chromium solutions due to high acidity and toxicity of hexavalent ions
present important drawbacks. But properties of chromium deposits are very interesting: until
now, it appears that all these properties are difficult (or impossible) to obtain by only one
alternative process. So it seems that the best alternative to chromium deposits is chromium
deposit itself but obtained in an environmentally friendly manner from trivalent chromium
solutions.
On another side different alternative processes have been explored trying to substitute Cr
electrodeposition. A (non-limitative) list could be given following the different publications
already done on the subject.
Process using physical processes or dry processes have been developed and are always on
progress in particular, these alternative processes have been or are studied in HCAT (Hard
Chromium Alternative Team) now termined and the associated following Research
programme ASETSDefense (Advance Surface Engineering Technologies for a Sustainable
Defense www.asetsdefense.org) which is a Department of Defense (DoD) initiative
sponsored by the Strategic Environmental Research and Development Program and the
Environmental Security Technology Certification Program. Its objective is to facilitate the
implementation of new, environmentally friendly technologies for surface engineering
(coatings and surface treatments) by providing ready access to background information and
technical data from research, development, test, and evaluation efforts as well as the status of
approvals and implementations.
One part of the program is devoted to the substitution of Chromium plating in aeronautic and
aerospace applications. Mainly, HVOF (High Velocity Oxygen-Fuel) thermal spray process
seems to be the most promising method but other method and processes are tested and
developed as PVD (Physical Vapour deposition processes), CVD (Chemical Vapour
Processes).
Some drawbacks bother the development of the processes in particular the NLOS (Non-Line
of Sight) surfaces, small parts, high costs, vacuum systems, adhesion problem and in some
cases environmental concerns due to powder toxicity.

In the same time, processes using liquid solutions (electroplating or electroless plating) have
been developed to substitute the use of hexavalent chromium.
The most important in the field is certainly the program developed at the beginning of 2000
years by Concurrent Technology Corporation in which different processes on the market have
been tested:
- Processes using trivalent chromium solutions (results have not been published)
- Processes using other metals (out of chromium) with nickel and without nickel salts.
In the last case(out of chromium) different processes have been compared : Ni(P), Ni-Co(P),
Co(P or B) electrolytic or electroless processes with and without particles, Cobalt micro and
nano-cristalline.
Following results, currently, Nickel electroless with particles seems to be the most promising
process in term of physical characteristics other processes presenting disadvantages :
- for the deposit characteristics as poor adhesion, wear and corrosion resistance weaker than
hard chromium
- for process itself, with increasing chemical complexity of the solution, cost of the products,
complex anodic reaction and degradation of compounds with formation of by-products,

So, the use of trivalent chromium solution seems to be intrinsically the most attractive process
and since a long time many attempts have been done trying to substitute hexavalent chromium
processes by trivalent chromium ones.
The first chromium metal has been obtained by electrodeposition in France. This first result
has been realized by electrolysis of an aqueous trivalent chromium solutions, published and
patented in 1848 by J unot de Bussy (1-2). R. Bunsen in 1854 (3) has studied the influence of
the catholic current density on the Chromium deposition using a hot chromium chloride
solution, with separation (porous pot) of anodic and cathodic compartments. The importance
of the separation between anodic and cathodic compartment has been a major results during a
long period and has been developed by others researchers as E. Placet & J . Bonnet (4) in
1901, J . Voisin (5) in 1910 and A. Recoura (6) in 1913.
Currently, decorative trivalent chromium processes are developed worldwide and deposits are
currently quasi indistinguishable in color from hexavalent deposits. Solutions used are
aqueous solution with trivalent chromium salts mainly chloride and/or sulfate with different
additive acting as complexant (formiates, thiocyanates, hypophosphites), different types of
wetting agents, and separation or not between anodic and cathodic compartment.
However, until now, there is no process to obtain at an industrial scale hard thick
chromium deposit through an aqueous trivalent chromium solution.

Why it is so difficult to deposit hard chromium from trivalent salts?
The different reasons to explain the lack of success have been enumerated in literature.
Among numerous publications, the reasons which seem the most important are:
- the high potential of Cr
3+
reduction to metallic state (-0.744 V/NHE) which explain in all
cases the high hydrogen evolution at the cathode,
- the stability of the hexa-coordinated (bipyramidal shaped) aqueous trivalent chromium
complex. The exchange kinetics of water molecules from Cr
3+
complex has been
evaluated and checked as 11 orders of magnitude weaker than for nickel complexes (7)
- chromium hydroxydes quickly precipitate and this phenomenon increases as the cathode
pH increases with the important hydrogen evolution
- formation of compounds by olation, oxolationas a function of the pH solution and
concentration in trivalent chromium, in particular near the cathode when the pH increases
due to hydrogen gaz formation by reduction of protons.
In the following presentation different processes to overcome the different difficulties will be
developed

II Different classes of process :

A Electroless chromium
Before describing the different electrolytic processes, it is clear that electroless deposition of
chromium would be a very suitable method for different reasons well understandable.
It has been published in 1955 that it is possible to deposit chromium using an electroless
method.
Two types of aqueous solution have been disclosed using hypophosphite and citrate ions,
chromium chloride and chromium fluoride with or without Glacial acetic Acid. Solutions are
working at 160-190F.
Following the publication, the deposition of electroless chromium is better on copper or brass
substrate and it is recommended for steel plating that a copper flash be realized before
chromium electroless plating. The solution, and so the process, is very sensitive to foreign
ions contamination.

B Electrolytic chromium
Currently, mainly two classes of processes are developed to overcome the moderate success
in hard thick trivalent chromium deposition :
processes using complexing agent to complex trivalent chromium ions in aqueous solution :
the processes are used in decorative applications. The complexation objectives are :
- to obtain lower potential reduction of Cr
3+
to metallic state
- to prevent the formation of hexa-aquo coordinated trivalent chromium complexes,
processes using chemical reduction of hexavalent chromium to obtain electrolytic solutions
of high concentration in Cr
3+
trivalent chromium. Cr(VI) reduction could be done using SO
2

or alcohol, to obtain trivalent chromium ions. In general, the Cr
3+
trivalent chromium is not
enclosed in very stable complexes.
It is interesting to note that using reduction processes allow to have trivalent chromium
solutions with high concentration in salt with a low pH.

1 Process using complexing agents :

These processes are used in decorative trivalent chromium applications, but it has been
extended to obtain at laboratory scale hard chromium layers..
These baths are using complexing agent as formate, thiocyanate or hypophosphite with in
some cases additives as : glycolic acid, citrates, sulfamates.
For each of these compositions the condition of deposition such as deposition rate, throwing
and covering power, microhardness, textureetcare different.

For solution using formiates several formulations have been proposed: in general the
Chromium salt used is chromium chloride with particular additives. We present in the
following text different formulations.
This is not an exhaustive list but a general approach of the different formulation with
complexant. We will present in another part the characteristics of trivalent chromium
processes using pulsed and/or cyclic current or using brush plating.
General Formiate process :
- CrCl
3
, 6 H
2
O: 100 -150 g/L - Wetting agent
- HCOOH: 50 80 ml/L - H
3
BO
3
: 10-40 g/L
- NH
4
Cl +NaCl: 70 -100 g/L
Deposition process :
- pH: 0.1 - 1 - Cathodic current density : 20 100 A/dm
- Temperature: 20 30 C

a Glycolic acid or citrate acid (8):
The composition of the solution is:
- CrCl
3
, 6 H
2
O 100 g/L - Glycolic acid 35 g/L or Sodium Citrate : 95 g/L
- HCOOH : 30 mL/L - H
3
BO
3
: 40 g/L
- NH
4
Cl : 80 g/L
Deposition characteristics :
- pH :1.5 - Cathodic current density : 30 50 A/dm
- Temperature: 20 50 C

b Sulfamates (9) :
For formate solution with sulfamate additives :
- CrCl
3
, 6 H
2
O 125 g/L - NH
4
NH
2
SO
3
: 180 g/L
- KCr(SO
4
)
2
: 25 g/L - wetting agent
- HCOOH : 60 mL/L
- NH
4
Cl : 80 g/L
Deposition Characteristics:
- pH :1.5 - Cathodic current density : 10-20 A/dm
- Temperature: 20 - 25 C

c Glycin (10)
- CrCl
3
, 6 H
2
O : 210 g/L - H
3
BO
3
: 35 g/L
- Glycin: 1.0 M - AlCl3: 50 g/L
- NaCl: 30 g/L - Wetting agent
- NH
4
Cl : 30 g/L
Deposition characteristics:
- pH : 0.1- 1
- Temperature: 30 - 50 C - Cathodic current density : 20 - 70 A/dm

d Hypophosphites (11):
- CrCl
3
, 6 H
2
O: 30-65 g/L - H
3
BO
3
: 15 g/L
- NaH
2
PO
2
: 200 g/L - Wetting agent
- NaF: 4 g/L -
- NH
4
Cl : 320 g/L
Deposition characteristics:
- pH : 2 5.5
- Temperature: 25 - 35 C - Cathodic current density : 2- 50 A/dm

e Thiocynates (12)
- Cr
2
(SO
4
)
3
, 6 H2O: 30-90 g/L - H
3
BO
3
: 20 - 40 g/L
- NaSCN: 25 - 80 g/L - Wetting agent
- Na
2
SO
4
: 200 g/L
Deposition process :
- pH : 2 3 - Cathodic current density : 2- 10 A/dm
- Temperature: 20 - 40 C

In general, these deposits have a microhardness of about 700 HV
100
, a cathodic efficiency
lower than hexavalent chromium processes and so a very slow rate of deposition (0.2 to
0.4m/min.).
However the covering power, cathodic current density zone in which fair metallic chromium
deposition takes place, is more important for those processes than for hexavalent.

2 Processes using trivalent salts obtained by reduction of hexavalent chromium ions:

a - Reduction by SO
2
(13)
The first application was done in 1946 by the U.S. Bureau of Mines (USA). This process
allows to prepare chromium metal by electrolytic deposition with anodic and cathodic
compartment separation.
- Cr
2
(SO
4
)
3
: 250 g/L (obtained by reduction of Na
2
CrO
4
by SO
2
)
- (NH
4
)
2
SO
4
: 40 g/L
- Na
2
SO
4
: 27 g/L
- (NH
4
)
2
S
2
O
8
: 100 200 mg/L (constant addition, function of electrolyse duration)
Deposition characteristics:
- pH : 1.8 2.2 - Cathodic current density : 6 A/dm
Temperature: 27 - 42 C

b - Reduction by alcohol (14):
- CrCl
3
: 130 180 g/L -Wetting agent
- NH
4
Cl: 50 100 g/L
- H
3
BO
3
: 30 50 g/L
Deposition characteristics:
- pH : <0 - Cathodic current density : 60 - 120 A/dm
- Temperature: 50C
The process allows deposition with high efficiency (up to 30%), deposits have a
microhardness of about 1000 HV
100
, the throwing and covering power are lower than other
processes. However these processes are interesting by the high rate of deposition (2-3
m/mn).
The bath obtained by the methanol reduction method is developed in our laboratory
This process is dangerous and hazardous, due to the high exothermic reaction of
hexavalent chromium reduction by alcohol.

3 Some particular processes:

Some interesting works have been developed on the influence of the current shape on the
deposit of chromium through trivalent solutions.
Results are depending on the shape of the cathodic current: the influence of the first layer and
the interface between cathode and solution is clearly demonstrated (15-16).
In general the electrolyte is from formiate complexant with different additives.
Condition of electrolysis are for example:
- Current density : 30 A/dm, Tc :80% - Ta: 20%, 100Hz. Current efficiency is 30-35% and
microhardness: 850HV (100g load)

Also some particular applications have been disclosed for brush plating which allows
depositing chromium layer on substrate using mobile systems (17-18). This application done
by Liquid Development Company could be of a major interest in the future to repair in situ
some default in chromium layers after wear or abrasion, or on default on chromium layer after
deposition.
The operating conditions :
- Formulation non-disclosed
- Dc: 6-15 A/inch - Voltage: 4 -15 V
- Temperature: 160-170F (for decorative purpose : room temperature)
- Anode to cathode movement: 40-60 ft/mn

4 Organic solvents: DMF and Ionic Liquids

During the first years of 1970 some processes using organic solvents (or mixed with water)
have been proposed, in particular solution made by DMF (Di-methyl Formamide) as a aprotic
polar solvent which decrease the formation and stability of aqueo-complex with Cr3+ions
and the H2 gaz evolution.
Results are very interesting but due to the toxicity of using large quantities of DMF they have
not obtained the industrial development linked with the performances.
More recently, following the development of the use of Ionic Liquids in particular for
electroplating during the IONMET European research programme (ended in 2009), research
have been done on hard chrome plating using trivalent chromium salts (19)
Using a mixed solution of CrCl
3
,6(H
2
O) and Choline Chloride, it is possible to realize hard
chromium layers on steel
The conditions are the following:
- Cr(Cl)
3
/ Choline Chloride : 1 / 2.5
- Temperature: 40C
- Cathodic Current Density : 15 A to 20 A.dm
-2

- Anode : platinised or Ir
2
O
3
titanium grill

Main results :
- Metallic and bright homogeneous aspect (darker than hexavalent processes)
- Cathode efficiency ~30 40 %
- Deposition rate ~0,7 to 1 m.min
-1
(15 A/dm)
- Hardness ~600 to 700 Hv
Some aspects of cross-sections of the deposit are shown in the following photographies


Fig.2 : Cross-section of Chromium deposits obtained by electrodepoition from Ionic
Liquids


The process seems to be robust and a replenishment method has been define following an
intensive use in the Laboratory.




III Influence of Thermal Treatment

Some authors have published information about the increasing of hardness in the case of
trivalent chromium (there is only few influence of the type of process deposition) by heat
treatment (20-21). In particular, in a research grant sponsored by AESF and published (22) it
has been shown the influence of thermal treatment on hardening of trivalent chromium.
Due to Cr
7
C
3
and Cr
2
O
3
formation during heat treatment (temperature 300-350 C and
duration 30 minutes), the microhardness is increased up to about 1700-1800 HV
100
for a
treatment : and in the same conditions the microhardness of hexavalent chromium deposits
decreased (cf. fig 2).
25 m 25 m 25 m
In particular it has been described through structural RX examination (23) that as soon as the
temperature reaches 290-300C, it appears that a structural modification takes place and that
there is a precipitation of chromium carbide : the chromium carbides formed prevents the
dislocations to move and so an increase of hardness occurs (pin effect).
Following figure 2, it appears clearly that the variation is fundamentally distincts and in the
case of trivalent chromium deposits, the variation is similar to variation of microhardness vs
temperature for electroless nickel.

Fig.2 : Evolution of the Hardness of the deposit (CrVI & CrIII) as a function of Heat Treatment


IV - Conclusions:

The history of alternative processes to hexavalent chromium is a long but not successful story.
Substitution of Hexavalent chromium processes by Trivalent ones seem to be the best way but
currently, no processes have obtained an industrial development.
Currently, the ionic liquids process seems to be the most promising but the adhesion of
chromium layer, as for all the trivalent processes, seems to be an obstacle for a large
industrial application.
Some utilisation, which does not require a strong adhesion, could be developped.
However, the question remains intact on the reason of substitution of hexavalent chromium in
hard chromium plating process: after deposition, there is no Cr(VI) on the parts and so the
only domain where the Cr(VI) risk is present is only in jobshop.
If the regulation in jobshop is well define and respected to avoid contamination of workers,
there is no real and serious reasons to banish hard chromium plating with Cr(VI)



2

h e u r es
4 h e u r es
8 h e u r es


Cr
III
C r
VI
Hardness (HV)
Temperature (C)
100 300 500 700
1800
BIBLIOGRAPHY

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5 J. Voisin Rev. Metall., 7,(1910), 1137
6 A. Recoura Comptes Rendus, 157, (1913), 1525
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th
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Birmingham (U.S.A.) 1946
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