Bright “White” Rhodium Plating

Title: Bright “white” Rhodium Plating of Decorative Components

S.Burling & D.Markey, E-CLAL UK, G.Bolli, E-CLAL Italy and S.Hemsley,
E-CLAL Singapore

Rhodium plating has been used for many years to provide a bright white finish
on decorative components. This paper will describe two new processes for these
applications, super white and ultra white as well as describing the development
of processes in this market. The operating conditions of these two new
processes will be described together with the results obtained from processes in
the field. The difference between super white and ultra white will also be
described.

S.Burling
Engelhard-CLAL UK Ltd.,
Valley Road,
Cinderford
Gloucestershire
GL14 2PB
UK

Tel: +44 1594 822181

Fax: +44 1594 822667

1
Introduction
The use of Rhodium plating as a “white” finish for decorative plated items has been a well
established process for many years.Over time attempts have been made to standardise the
colour/whiteness of the Rhodium deposit. This paper is an attempt to clarify a measurement
technique of the “whiteness” in comparison with the most sophisticated technique available,
the human eye.

History Of Rhodium Plating

Rhodium, (Greek - Rhodon, Rose), is one of the rarest elements, it constitutes only around
1 x 10-7 of the earth’s crust.
Rhodium was discovered in 1803-4 by Woolaston2, in crude platinum ore believed to be
obtained from South America.
It is found in small quantities associated with all native platinum; in the minerals, rhodite,
sperrylite, iridosamine and in some nickel-copper ores.
Rhodium occurs naturally with other platinum metals, the rivers sands of the Urals and also in
North and South America.
The annual world production of rhodium is only around 7 - 8 tons.
Its scarcity, difficulties with extraction and purification, combined with the fact that the other
precious metals were more abundant, easier to work with and satisfied the industrial demands,
meant that progress on the electrochemical nature of rhodium was slow.

No significant work was carried out until the late 1920s when the chemistry of rhodium began
to be explored on many fronts.
Practical methods for separation of the metal were described by Wichers and Gilchrist in
19283, from that date onwards, many references exist related to rhodium as workers began to
explore the electrochemical properties.
Keitel and Zschiegner4 were among the early workers and developed a solution analogous to
their platinum bath with the rhodium in the form of dinitro-diammino nitrite (US patent
1,779,436 and 1,779,457 [1930]).
Also among the early workers were Fink and Lambros5 (1933) who explored the possibility of
a bath using rhodium hydroxide in a sulphuric acid electrolyte. They also explored the
addition of supplementary organic acids.
Atkinson and Raper6 (1934) proposed an acid bath using rhodium amminonitrite which could
incorporate additions of sodium nitrite to enhance the conductivity and help to stabilise the
rhodium amminonitrite in the electrolyte.
As technology developed, then many workers7,8,9 explored the chemistry and two basic
electrolytes emerged, based on either Rhodium Sulphate in a Sulphuric Acid electrolyte or
Rhodium Phosphate in a Phosphoric Acid Electrolyte.
Reid8 and Rhodes10 investigated a variety of electrolytes and some examples are shown in
Table I.
It can be seen that the rhodium metal content of these earlier baths was significantly higher
than the presently available commercial plating baths, which normally will operate at below
5 g/l rhodium for economic reasons rather than any intrinsic technical benefit.
A general trend that was observed by Reid8 was that sulphate baths always exhibited a higher
cathode efficiency than the phosphate baths and that sulphate baths also exhibited lower
internal stress and marginally higher hardness values.

2
Sulphamate baths showed some positive aspects, but did not generate sufficient commercial
interest for their parameters to be fully optimised.
Addition agents to maintain the whiteness of rhodium were explored in the early stages of
process development11, many of these additives were organic material believed to enhance the
whiteness of the rhodium deposit, some of these organics were patented12.
The purity of the rhodium used in the manufacture of the plating syrup is known to have a
significant effect on the final whiteness of the electrodeposit, metallic impurities, in particular,
will degrade the whiteness of the final rhodium electrodeposit. Any metallic contaminants
introduced to the plating bath during production plating will also serve to degrade the
whiteness. This subject will be referred to later.
A common contaminant in costume jewellery production is nickel which traditionally has
been a common undercoat for costume jewellery items, normally a rhodium bath will show a
decrease in whiteness with increase in nickel concentration.
European legislation to reduce the usage of nickel13 in many of these applications may reduce
the possibility of this contaminant.
Three types of rhodium baths have emerged as the most established processes14.
Some typical formulations used for decorative applications are shown below.
1. Sulphate bath
Rhodium (as sulphate concentrate) 2 g/l
Sulphuric Acid (conc.) 20 ml/l
2. Phosphate-Sulphate
Rhodium (as phosphate concentrate) 2 g/l
Sulphuric Acid (conc.) 20 ml/l
3. Phosphate bath
Rhodium (as phosphate concentrate) 2 g/l
Phosphoric Acid, ortho 85% 40 ml/l
All of these baths are operated in the range 1 - 4 A/dm2, using platinum or platinised titanium
anodes.
The sulphate bath has been found to exhibit a lower stress15 and as such is often the basis for
industrial applications where a thicker deposit (1.0 - 5.0 microns) of rhodium is often
employed.
Rhodium, as plated, is a highly stressed deposit, so for these thicknesses a stress reducer is
often employed in proprietary formulations, some examples are selenic acid and magnesium
sulphamate14.
Rhodium baths due to their very nature are very susceptible to contamination, both organic
and metallic. In decorative baths this can show itself as a darkening of the deposit and by
exhibiting stress in industrial deposits.
Steps should be therefore be taken to ensure any carryover or drag-in of contamination from
preceding plating stages is eliminated, this can be by use of fully effective rinsing techniques
and employing clean de-ionised or distilled water rinses immediately prior to the rhodium
bath.
It should be remembered that rhodium baths are acidic and will readily attack many base
metals if they are exposed to the solution, care should be taken in tank design to eliminate any
exposed metal parts from contact with the solution.
Rhodium is one of the Platinum Group of metals. Some of the basic physical properties of
rhodium are shown in the following Table II.

3
Examining Colour
An infinite number of colours surround us in our everyday lives. We all take colour
pretty much for granted and it has a wide range of roles in our daily lives.
A colour expression often though means ten different colours to ten different people.
If you show the same plated item to different people you are bound to get different
answers describing the colour.
Colour is a matter of perception and subjective interpretation. Even if they are
looking at the same plated item different people will draw on different references and
experiences to express colour in different words.
Words for expressing colour have always changed with the times. Words like
“electric” to describe a colour could not have been used before the invention of
electricity. Adjectives such as “bright”, “dull” and “deep” are often used to improve
the description.
Therefore verbal expression of colour is still not accurate enough. How then shall
colours be expressed to avoid misunderstandings?
Even when we just look around, a wide variety of colours leap into our eyes. We are
surrounded by an infinite variety of colours in our daily lives. However, unlike
length or weight, there is no physical scale for measuring colour, making it unlikely
that everyone will answer in the same way when asked what a certain colour is. For
example, if we say “blue ocean” or “blue sky” to people, each individual will
imagine different blue colours, because their colour sensitivity and past experiences
will be different.

This is the problem with colour. If there was a standard method by which colours
could be accurately expressed and understood colour communication could be
smoother, simpler and exact.
Such precise colour communication could if applied to rhodium plated items
eliminate colour related problems.
So let’s study a little and determine what kind of colour information would be useful.

Factors that affect how a colour looks.

Light-source differences
Most people have experienced how sunlight, fluorescent light, tungsten light, etc.: each type
of illumination will make the same plated item look different.

Observer differences
The sensitivity of each individual’s eyes is slightly different; even for people considered to
have “normal” colour vision, there may be some bias toward red or blue. Also, a person’s
eyesight generally changes with age. Therefore the same colour can appear to be different to
different people.

Size differences
Colours covering a large area tend to appear brighter and more vivid than colours covering a
smaller area. This is referred to as area effect. Selecting objects which will have a large area
based on colour samples having a small area may result in mistakes.

4
Background differences
If a plated item is placed in front of a bright background, it will appear duller than when it
was placed in front of a dark background. This is referred to as contrast effect, and is
undesirable for accurately judging colour.

Directional differences
Often when looking at a plated item, viewing from a slightly different angle can make the
item appear brighter or darker. This is due to the directional characteristics of the plated item.
The angle from which the object is viewed, and also the angle from which it is illuminated,
must be constant for accurate colour identification.

The Principles of Colour.

Hue. Lightness. Saturation .
Red. Yellow, Green, Blue…
Hue Hues form the colour wheel.
Apples are red, lemons are yellow, the sky is blue; that’s how we all think of colour in
everyday language. Hue is the term used in the world of colour for the classifications of red,
yellow, blue, etc. Also, although yellow and red are two completely different hues, mixing
yellow and red together results in orange (which is sometimes referred to as yellow-red),
mixing yellow and green results in yellow-green, mixing blue and green results in blue-green,
and so on. The continuum of these hues results in the colour wheel shown in Figure 1.

Bright colours, dark colours.

Lightness The lightness of colours changes vertically.

Colours can be separated into bright and dark colours when their lightnesses (how bright they
are) are compared. Take, for example, the yellows of a lemon and a grapefruit. Without a
doubt, the yellow of the lemon is much brighter. How about the yellow of a lemon and the
red of a sweet cherry. Again, the yellow of the lemon is brighter, right? This lightness can be
measured independently of hue. Now take a look at Figure 2. This figure is a cross section of
Figure 1, cut along a straight line between A (Green) and B (Red-purple). As the figure
shows, lightness increases toward the top and decreases toward the bottom.

5
Saturation Vivid colours, dull colours.
Saturation changes outward from the centre.

Going back to yellow, how do you compare the yellows of a lemon and a pear? You might
say the yellow of the lemon is brighter, but more to the point in this case, it is vivid, while the
yellow of the pear is dull. This is another big difference, but this time one of colour saturation
or vividness. This attribute is completely separate from those of both hue and lightness. If
we look at Figure 2 again, we can see that saturation changes for red-purple and green
respectively as the horizontal distance from the centre changes. Colours are dull near the
centre and become more vivid as we move away from the centre. Figure 3 shows general
adjectives used to describe the lightness and saturation of colours. To see what the words
express, look back at Figure 2 again.

By creating scales for hue, lightness, and saturation, we

can measure colour numerically.

History of expressing colours numerically.

Various people in the past have devised methods, often using complex formulas, for
quantifying colour and expressing it numerically with the aim of making it possible for
anyone to communicate colours more easily and more accurately. These methods attempt to
provide a way of expressing colours numerically, in much the same way that we express
length or weight. For example, in 1905 the American artist A. H. Munsell(17) devised a
method for expressing colours which utilised a great number of paper colour chips classified
according to their hue (Munsell Hue), lightness (Munsell Value), and saturation (Munsell
Chroma) for visual comparison with a specimen colour. Later, after a variety of further
experiments, this system was updated to create the Munsell Renotation System, which is the
Munsell system presently in use. In this system, any given colour is expressed as a
letter/number combination (H V/C) in terms of its hue (H), value (V), and chroma (C) as
visually evaluated using the Munsell Colour Charts. Other methods for expressing colour
numerically were developed by an international organisation concerned with light and colour,
the Commission Internationale de l’Eclairage (CIE).

The two most widely known of these methods are the Yxy colour space, devised in 1931(18)
based on the tristimulus values XYZ defined by CIE, and the L*a*b* colour space, devised in
1976(19) to provide more uniform colour differences in relation to visual differences. Colour
spaces! such as these are now used throughout the world for colour communication.
!
Colour space(20) Method for expressing the colour of an object or a light source using some kind of
notation, such as numbers

The L*a*b* colour space method.

The L*a*b* colour space (also referred to as CIELAB) is presently one of the most popular
colour space for measuring object colour and is widely used in virtually all fields. It is one of

6
the uniform colour spaces defined by CIE in 1976 in order to reduce one of the major
problems of the original Yxy colour space: that equal distances on the x, y chromaticity
diagram did not correspond to equal perceived colour differences. In this colour space, L*
indicates lightness and a* and b* are the chromaticity co-ordinates. Figure 1 shows the a*, b*
chromaticity diagram. In this diagram, the a* and b* indicate colour directions: +a* is the red
direction, -a* is the green direction, +b* is the yellow direction, and -b* is the blue direction.
The centre is achromatic; as the a* and b* values increase and the point moves out from the
centre, the saturation of the colour increases. Figure 1 is a view of this solid cut horizontally
at a constant L* value.

Plating Test Procedure

Three solution formulations were chosen to evaluate for their colour differences. They were
as follows :
1) Rhodium Phosphate, Sulphuric Acid Type. Standard Rhodium No Additive.
2) Rhodium Sulphate, Sulphuric Acid Type. Pure Rhodium With Additive A (Super White).
3) Rhodium Sulphate, Sulphuric Acid Type. Pure Rhodium With Additive B (Ultra White).

The test panels were evaluated for their differences with Current Density, Thickness of
Deposit and for low levels of contaminants.
The formulation for each bath was as in Table III and the results of the colour measurements
tabulated in Table IV.

The method of Colour Measurement using the Minolta

Chromameter CR200

This procedure relates to standard white plate calibration.

Absolute colour measurements are made in L* a* b* co-ordinates in the

Munsell colour system.
L* = Light/Darkness
+a* = Red. -a* = Green
+b* = Yellow. -b* = Blue

Equipment
Minolta Chromameter CR200, Measuring Head, AC adaptor and White
calibration plate.

Calibration
Interval - before use.
Slide power switch on.
Display should show:

END Y94.20
x .3156 y.3330

If not, press COLOUR SPACE SELECT to obtain.

7
Place measuring head on the white calibration plate and press CALIBRATE
and wait for the 3 flashes of the pulsed Xenon arc lamp. Do not remove the
measuring head until the 3 flashes have pulsed. The Minolta will average the 3
readings and the display should now show:

CAL. Choo Y94.20

x .3156 y.3330

If the calibration is incorrect, move the cursor marked ← / →, and then enter
the corrected values for Y, x, y.

When the correct values for Y, x, y have been entered, press COLOUR
SPACE SELECT to give the L*, a*, b* display. The Chromameter is now
ready for use.

8
COLOUR EVALUATION OF RHODIUM: Phosphate, Super White & Ultra White.

Minolta - L*a*b* results (Results for 0.5 & 1.0 micron compared)

1) Colour difference (Delta E) between Phosphate & Super White = 0.73 & 1.21 according to the
classification is small.

2) Colour difference (Delta E) between Super White & Ultra White = 0.46 & 0.94 according to the
classification is again seen as small.

Up to 0.2 - Not perceptible

0.2 - 0.5 - Very small
0.5 - 1.5 - Small
1.5 - 3.0 - Distinct
3.0 - 6.0 - Very distinct
6.0 - 12.0 - Great
above 12 - Large

Visual Results

A number people were separately shown panels of Phosphate type, Super White & Ultra White that
were labelled as A,B & C

and asked their opinion on the colour difference. The results were as follows :

A = Phosphate B = Super White C = Ultra White.

1) 20 % Could not see any difference between any of the three panels.

Of the other 80% the following was established.

2) A has a yellow / orange tinge. Obvious difference in lightness between A & B or A & C.
A slight yellow tinge is also seen in B. There is a subtle difference in colour for panel C
compared to panel B.

3) A has a gold tinge. Panels B & C look slightly lighter & greyer in appearance. No difference
seen between panels B & C.

4) A is darker in appearance than B or C. Only a subtle difference in lightness is seen between

B & C.

5) A looks yellow / brown in colour compared with B & C. No significant difference seen between
B & C.

CONCLUSIONS

* The results from the Minolta fails to pick up the colour differences, that the human eye can quite
clearly see ie. between Phosphate & Super White or Phosphate & Ultra White.

9
* However, If you look at the 0.5 & 1.0 micron thickness results, the Minolta does appear to have
picked up a very small difference between Phoshate Type, Super White and Ultra White.

* Out of the contaminants added to the solution (Ni,Cu,Fe, and Ag) at 20ppm and 100ppm, only
the Ag (at low ppms) seemed to have any effect on the colour, causing it to darken or turn black.
It is well known that as nickel contamination in the Rhodium bath increases the deposit will
gradually darken. Due to the acidic nature of the bath this is inevitable.

* The human eye is more accurate than the Minolta, as most people can see a definite difference
in colour between Phosphate, and the other two Rhodiums. The Minolta's numerical results are all
very close, and does not pick up any significant difference.

* Studies have shown that over 90% of humanity have a fairly close correlation of colour
discimination, so there can be a general agreement as to colour matches in most cases.
The minolta only appears to pick up on the greyness in the panels, and does not see any significant
differences in the colour between the panels. The human eye therefore still seems the more
reliable method of establishing the "colour or whiteness". Unfortunately we still are subject to
subject to human preferences, therefore there will perhaps always be the discussion on how
white is a "white" Rhodium. White, Grey-White, Yellow-White and Blue-White all seem to be
relevant.

10
 Table I

Some Examples of Early Rhodium Electrolytes Investigated by

Reid and Rhodes

Electrolyte Type Unit Rhodium Free Acid

Concentration Concentration
Sulphate g/l 10 - 50 10 – 100

Phosphate g/l 10 - 50 30

Sulphate - Phosphate g/l 20 10 – 100

(Mixed Acid)

Fluoborate g/l 20 - 90 25

Sulphamate g/l 20 - 50 30

11
 Table II

Properties of Rhodium

Property Unit Value

Chemical Symbol - Rh

Atomic Number - 45

Atomic Weight - 102.905

Specific Gravity at 25°C - 12.41

Hardness Hv 700 – 800

Physical State at 25°C - Solid, metal

Melting Point °C 1964 ± 3

Boiling Point °C 3695 ± 100

Electronegativity Pauling 2.28

Crystal Structure - Face Centred Cubic

Weight Deposited / ampere hour @ g 1.28

100% Cathode Efficiency

12
 Table III

Formulation of the Solutions.

Electrolyte Type Phosphate Sulphate Sulphate

(Super White) (Ultra White)
Rhodium Concentration 2g/l 2g/l 2g/l

Sulphuric Acid Concentration 20m/l 25ml/l 15ml/l

Phosphoric Acid Concentration 20g/l - -

Additive X Y Y

Temperature oC 40 25 25

13
 COLOUR EVALUATION OF RHODIUM PLATING SOLUTIONS TABLE IV

All colour measurments obtained using the Minolta Chromameter CR200, using the L*a*b* Colour Notation System.

C* = Colour Tone Delta E = The degree of colour difference

Rhodium Phospate Type Rhodium Sulphate Type (Super White) Rhodium Sulphate Type (Ultra White)

L* a* b* Delta E Diff. from Chroma L* a* b* Delta E Diff. from Chroma Phosphate L* a* b* Delta E Diff. Chroma
Std. C*= a2 + b2 Std. C*= a2 + b2 Compared with from Std. b2
SW

Standard 0.1 microns 73.89 0.96 1.85 73.92 - = darker 2.08 73.06 0.97 1.76 73.09 - = darker 2.00 0.83 74.59 0.95 1.51 74.61 -= 1.23
than std. Very Pale Grey than std. Very Pale Grey darker Pale Gre
+ = lighter + = lighter than std.
than std. than std. +=
lighter
than std.
Change in C.D 1 A/dm2 73.12 1.14 2.59 73.17 -0.75 2.83 72.66 1.00 2.21 72.70 -0.39 2.42 0.47 74.36 1.10 1.51 74.38 -0.23 1.23
Very Pale Grey Very Pale Grey Grey

2 A/dm2 73.30 1.03 2.14 73.34 -0.58 2.37 72.38 1.28 1.90 72.42 -0.67 2.29 0.92 74.16 1.28 1.41 74.18 -0.43 1.90
Very Pale Grey Very Pale Grey Grey

3 A/dm2 73.44 1.03 2.47 73.49 -0.43 2.68 73.28 1.13 1.77 73.31 0.22 2.10 0.18 74.51 1.08 1.34 74.53 -0.08 1.72
Very Pale Grey Very Pale Grey Grey

4 A/dm2 73.28 1.01 2.21 73.32 -0.60 2.43 74.10 1.18 1.59 74.13 1.04 1.98 0.81 74.71 1.08 1.23 74.73 0.12 1.64
Very Pale Grey Very Pale Grey Grey

5 A/dm2 73.87 1.05 1.60 73.89 -0.03 1.91 73.42 1.20 1.61 73.45 0.36 2.01 0.44 74.49 0.96 1.42 74.51 -0.1 1.71
Very Pale Grey Very Pale Grey Grey

Change in Thickness microns 73.89 0.96 1.85 73.92 std. 2.08 73.06 0.97 1.76 73.09 std. 2.00 0.83 74.59 0.95 1.51 74.61 std. 1.23
0.10 Very Pale Grey Very Pale Grey Grey

0.25 72.85 0.95 2.72 72.91 -1.01 2.88 73.47 1.15 1.70 73.50 0.41 2.05 0.59 74.14 1.03 1.73 74.17 -0.44 2.01
Very Pale Grey Very Pale Grey Grey

0.50 72.60 0.95 2.79 72.66 -1.26 2.95 73.38 1.23 0.72 73.39 0.30 1.42 0.73 73.83 0.98 1.60 73.85 -0.76 1.88
Very Pale Grey Very Pale Grey Grey

1.00 71.89 1.24 2.84 71.96 -1.96 3.10 73.14 1.14 1.89 73.17 0.08 2.21 1.21 74.08 1.07 1.68 74.11 -0.44 1.99
Very Pale Grey Very Pale Grey Grey

Added Impurities 20ppm 74.27 1.15 1.50 74.29 0.37 1.89 75.12 0.77 1.07 75.13 2.04 1.32 0.84 74.52 1.10 1.30 74.54 -0.07 1.70
Nickel Very Pale Grey Very Pale Grey Grey

100 ppm 74.44 1.21 1.41 74.46 0.54 1.86 73.28 0.97 1.59 73.30 0.21 1.86 1.16 74.10 1.10 1.51 74.12 -0.49 1.87
Nickel Very Pale Grey Very Pale Grey Grey

20ppm 74.11 0.84 1.42 74.13 0.21 1.65 73.70 1.12 1.49 73.72 0.63 1.86 0.43 74.47 0.94 1.65 74.49 -0.12 1.90
Copper Very Pale Grey Very Pale Grey Grey

100 ppm 72.84 0.73 1.85 72.87 -1.05 2.0 72.19 1.04 2.04 72.23 0.86 2.29 0.64 73.65 0.92 1.80 73.68 -1.03 2.02
Copper Very Pale Grey Very Pale Grey Grey

20 ppm 73.91 1.03 1.55 73.93 0.01 1.86 73.69 1.17 1.45 73.71 0.62 1.86 0.22 73.56 0.83 1.92 73.58 -1.03 2.09
Iron Very Pale Grey Very Pale Grey Grey

14
100 ppm 74.34 0.93 1.29 74.36 0.44 1.59 73.43 1.16 1.59 73.46 0.37 1.97 0.93 72.24 0.89 2.15 72.27 -2.34 2.33
Iron Very Pale Grey Very Pale Grey Grey

20ppm 74.57 0.85 0.81 74.58 0.66 1.17 73.77 1.09 1.43 73.79 0.70 1.80 0.79 72.40 0.77 2.61 72.45 -2.16 2.72
Silver Very Pale Grey Very Pale Grey Grey

100 ppm 23.92 1.72 3.92 24.30 49.62 5.2 70.33 1.08 3.85 70.44 -2.65 4.00 46.14 65.90 0.73 2.32 65.94 -8.67 2.43
Silver Very Dark Grey / Greyish / Dark Dark
Black

15
 Figure 1: Colour wheel
Hue. Lightness. Saturation.

Ye

ge
The world of colour

ll o

an
w

Or
Ye
ll o d
w Re
-g r
ee
n is a mixture of
(A)
Green Red-purple (B)
these three attributes.
g re
en B lue Pu
rp
e-
B lu le
- pu r
e
B lu

ple

Figure 2: Changes i n lightness and saturation for red-purple & green

High
Figure 3:
Adjectives related to colours
(for lightness and saturation)
L
i
g white
light pale pale
h
B light
t A
bright
n bright
e
s
s vivid/strong greyish/weak greyish/weak vivid/strong
(A) dull dull (B)

deep
Low deep

High Low High dark dark

Saturation Saturation
black

16
References

1. The Merck Index 12th Edition (1996).

2. Phil. Trans 94.419.(1804).
3. Wichers & Gilchrist Trans Am Mining Metallurgical Eng 76,619, (1928).
4. W. Keitel and H.E. Zschiegner Elektrochem, 39.948-58 (1930).
5. C.G. Fink and G.C. Lambros Trans Electrochem. Soc.63 181-6 (1933).
6. R.H. Atkinson and A.R. Raper Metal Ind.(N.Y.) 32,119-21 (1934).
7. K. Schumpelt Electrochem.Soc 80,495 (1941).
8. F.H. Reid Bull.Inst.Metal Finishing 6,107-42 (1956).
9. H.J. Wiesner Proc.Amer.Electroplat.Soc 39,79-99 (1952).
10. E.A. Parker Plating, 1955,42,882-92 (1955).
11. S. Dorner and L. Froels Galvanotechnik.49.539 (1948).
12. Baker, US Pat 2,057,475 (1936).
13. S.J. Hemsley & J.F. Sargent Nickel Free Plating Technology for Decorative
Applications. AESF SURFIN98 Conference Minneapolis 185-193 (1998).
14. Frederick.A.Lowenheim, Modern Electroplating, Electrochemical Society, Princeton
NJ. Page 351 Third Edition (1974).
15. F.H. Reid, Metall.Rev, 8,167 (1963).
16. G.R. Smith, C.B. Kenahan, R.L. Andrews and D. Schlain, Plating, 56,805 (1969).
17. A.H.Munsell (1905) Method of expressing colours.
18. CIE (1931) Method of expressing colours.
19. CIE (1976) Method of expressing colours.
20. Minolta Handbook (1993) P colour contamination.

17