contro|, analysis, and testing

T E S T CELLS F O R P L A T I N G
BY DAVID R. GABE
INSTITUTE OF POLYMERTECHNOLOGY AND MATERIALSENGINEERING,
LOUGHBOROUGH UNIVERSITYOF TECHNOLOGY, LOUGHBOROUGH,
LEICESTERSHIRE,U.K.; www.tboro.ac.uk/departments/iptme

Plating cells are employed to define the link between processing conditions and
deposit properties and characteristics for electrodeposition.
ProcessParameters:
Solution concentration
Conductivity, pH
Temperature
Current density
Voltage/potential
Deposit Parameters:
Composition/purity
Thickness uniformity
Smoothness, brightness
Hardness, ductility, strength
Grain size
The electroplater needs a rapid and convenient test method to give a good, not
necessarily precise, indication of this interaction and, in particular, to indicate any
departure From perceived optimum process conditions and then provide the
means of correcting that departure. A number of cells have been devised to give
such a convenient link. They attempt to correlate the parameters of prime con-
cern-composition and current density-with deposit thickness and thickness dis-
tribution. Figure 1 and Table I illustrate this choice.
Some of the cells in Fig. i and Table I have very specific applications, e.g., D and
K for chromium plating, where the throwing power (TP) is poor and the CrO3:SO4
catalyst ratio is critical. Two (B,F) have been adopted for wider use on account of
their versatility.

H A R I N G - B L U H CELL
This cell was devised as a TP cell and consists of a long, narrow plating box with

Table I. Design and Function of Plating Cells Shown in Fig. 1

Example Design Purpose
C,D Bent cathode cells Throwing power and recess plating
A,B,I Hull cells Current distribution and deposit appearance
J,K Slot cells Slot acts as a point anode
F Haring-Blum cell Throwing power (TP) and TP index determination
A,C,E,F,G Variable geometry Combined cells
H Current efficiency cell Uniform deposition for cathode current efficiency
measurement

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 \ll A
o Ill 6

+
+

+ - I ,.

d
! +

II Ii
I I +

Fig. 1. Test cells used in electroplating control.

one central movable anode and two cathodes placed at relative distances, typically
of 5:1 from the anode. TP is calculated from a formula, the classic Haring version
being:
% TP = 100 (L-R)/L
where L is the far-to-near cathode distance ratio and R is the ratio of weights
of deposits on the cathodes.
The experimental principle is well established, but a number of alternative for-
mulas have been used primarily to either give a symmetrical TP scale or to
expand the scale at specific ranges. Three other TP index formulas in use are
Healey
% T P = 100 (L- M/(L- 1)

Field:
% TP = 100 (L- M/(L+M - 2)

Subramanian:
% TP = 100 (L- M)/M(L- 1)
Of these formulas, that of Field has been most widely used and is incorporated
in some standards (e.g., British Standard 205 part 5), with L = 5:1, largely because

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 Table II. Throwing Power Indices for Various Values of M
M Haring-Blum Heatley Field Subramanian
1 80 100 100 100
2 60 75 60 37.5
3 40 50 33.3 16.7
5 0 0 0 0
10 -100 -125 -38.5 -12.5
100 -1,900 -2,375 -92 -23.75
. . . . . 100
. -25

the values of TPcan vary from + 100 to -100, with a value ofTP = 0 when the cur-
rent and metal distribution are equal. This scale gives the poorest TP of[-100%
(as } 9t when there is no metal deposited on the far cathode) and the best TP of
+100% (for M = 1). If metal distributes according to the length ratio (e.g., M = 5
when L = 1), the TP is 0. Values of the TP index for each formula are tabulated in
Table II for the Haring-Blum cell and several others.
Chin has proposed a logarithmic index, such that M = 1 when L = 1, which
would yield more convenient numbers for the index values. Chin's definition is:
Logarithmic TP = Log L/Log M
Graphic and computerized methods have also been developed.

HULL CELL
The Hull cell provides four basic facilities for the electroplater in plating process
control: optimization for current density range; optimization of additive con-
centration; recognition of impurity effects; and indications of macro-throwing
power capability.
The c o m m o n type of Hull cell is the 267-ml trapezoidal container utilizing a
4-in. (10.2-cm) cathode panel inclined at 38 ° to the parallel sides and having a 2-
in. (5.1-cm) anode, which may be corrugated to increase its electrode area_ A solu-
tion depth of 2 in. (5.1 cm) gives a volume of 267 ml; a 3-in. (7.6-cm) depth would
give a volume of 320 ml. Figure 2 illustrates the form of the standard cell. The
dimensions are important to give the following relationships:
267-mi cell: 2 g addition is equivalent to 1 oz per U.S. gal
320-ml cell: 2 g addition is equivalent to 2 oz per Imperial gal

The cell can be made of a number of materials, including Perspex, Lucite,

polypropylene, or glazed porcelain, depending upon the temperature of usage
and the corrosivity of the elec-
ANODE FCATHODE trolyte. It is nowadays usual to
"~ ~ 1 7/8" , / supply them as a plain box with
incorporated air bubbler or with
incorporated thermostatic heater.
2 6 7 ml The standard cell current is 2
SOLUTION A, which gives a current density

LL_
2 1/2"

I. -5" .I
I

I
LEVEL
range of 2.4-84 A/ft 2 (0.26-9
A/dm 2) corresponding to anode-
to-cathode spacings of 5 to i in.,
Fig. 2. Dimensions of the Hull cell.
respectively. The cell is calibrated

513
 I I I
by using thickness profiles of
14
the cathode panel and assum-
12 ing appropriate current effi-
3A ciencies, such data yielding a
tO calibration graph having curves
.<
2A for 1, 2, 3, etc.-A cell currents
8
(see Fig. 3). If preferred, a for-
6 mula may be derived having the
following form:
4
ill/ = Iappl(a-b log L)
2
where ill/ is the current den°
2.5 5.0 7.5 10.0 sity at a distance L; Iappl is the
total cell current employed; L is
Distance from high current density end, cm.
the length along the panel; and
Fig. 3. Calibration graph for a Hull cell with cell a,b are constants requiring cal-
currents of 1, 2, and 3 A.
ibration. Using inch and A / f t 2
units, a = 27.7 and b = 48.7; if
cm and A/cm 2 are used, a = 5.10 and b = 5.24.
Other sizes of Hull cell, which have been employed for specific purposes and
calibrations, would be:
3 x 5-in. panel with 2.5-in solution depth a =18.8; b = 28.3
6.4 x 10.2-cm panel with 5-cm solution depth a = 5.10; b = 5.24
In all cases, extremities of the cathode panel should be neglected and every
attempt made to eliminate solution impurities, residues, etc. and to maintain a
consistent procedure with a standard time of plating, typically 2 or S min (for S
and 2 A, respectively). Means of temperature and agitation control can be built
in for the same reason.
Interpretation of the cathode panels relates to three pieces of derived information.
1. Establishment of the optimum plating current density range by means
of the graph, formula, or various charts. For this purpose, a mid-height
line should be taken to minimize stagnation effects at the cell bottom and
to avoid emphasizing convection effects at the top meniscus.
2. Establishment of the additive level required to create bright or level deposit
zones preferably at the center of the panel. For this purpose, aliquots of 0.5
or 1.0 g are added to the cell, mixed in, and the effect noted.
3. Recognition of atypical appearances attributable to the presence of
impurities in solution or to additive degradation products. Experience
frequently indicates an appropriate remedy and suppliers of propri-
etary processes should provide guidance notes.
A number of coding and diagrammatic systems have been used for the panel's
appearances (see Fig. 4). The panel demonstrates, in zones from left to right, high-
, medium-, and low-current density appearances corresponding to burned/nodu-
lar, semibright/bright/leveled to dull, or no deposit zones. The presence of addi-
tives will eliminate extremes of burning and powdery/dendritic deposit formation
and ideally widen the leveled/bright zone into a practicable working range of cur-
rent density at that temperature and solution concentration.

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 BRIGHT P L A T I N G ADDITION AGENT-NONE

A.A. 50 % OF" O P T I M U M

W//A t----I
A.A. OPTIMUM

V/A
A.A, 150% OF OPTIMUM

DAR...K BRIG.HT CRACKED

A.A. 2 0 0 % OFOPTIMUM
GR AY PITTED NO PLATE oo
oo ×y

Fig. 4. Diagrammatic system for reporting Hull ceil behavior.

MODIFIED CELLS
Each of the basic cells has a number of limitations that have been recognized, but
which do not detract from usage as "qualitative procedures to provide quantitative
information," however, in a number of specific cases, the limitation could be more
serious; for example, temperature control may be poor and metal ion concen-
trations may change if the test extends over a few minutes. Various modifications
have, therefore, been employed, which, for the Hull cell, can be enumerated as in
Table III.
The most serious shortcoming relaxes to the use of agitation to enhance depo-
sition rates in high-speed electrodeposition processes when a correlation factor of
5 to 50 times may apply between the "static" Hull cell and the "dynamic" plating
tanks. This factor can be determined typicallyby comparing bright plating ranges
for the Hull cell with those identified for the tank; recently, however, several pro-
posals have been made for current density distribution cells incorporating electrode
rotation as a convenient means ofquantitaxive agitation. They utilize rotating cone
electrodes; rotating cylinder electrodes; or rotating electrodes in baffled cells.
In general, all appear to be reasonably effective, but each requires development
work in the context of a particular application to establish its credibility.

TEST CELLS AND TROUBLESHOOTING

A number of applications for test ceils have been identified, which may conve-
niently be classified as troubleshooting. In most cases, the most successful use of

Table III. Modifications to the HuU Ceil

Design Authors
Hanging cell to be suspended in a tank Mohler ~
Skwirzynski and Huttley~
Flat cathode but curved anode to yield a linear current density Gilmont and Walton ~
to L relationship
Circulating electrolyte pumped along cathode plate at Dimon 4
controlled velocity
Nonvertical cathode to counter natural convection Esih 5
Segment of a concentric cell with cathodes at either end Teraikado and Negasaka6
and variably positioned anode

515
the cells is when the solutions or processes in question have been fully charac-
terized when known to be in a first-class working order. This clearly suggests that
each solution should be fully studied when first used and a set of reference
panels and data prepared for regular use. (It is usually advisable to lacquer such
panels or otherwise protect them in sealed polymer envelopes in order to provide
adequate shelf life.) It is also worth noting that each metal and solution type has
its own character, which experience will define only too well.
The test cells, particularly the Hull cell, can be used to identify noncharacteristic
behavior under several categories.
1. Establishment of the optimum current density range.
2. Recognition of the effect of variation of temperature, pH, presence of
impurities, changes in solution concentration, especially critical com-
ponents such as conductivity salts or catalysts in hexavalent chromium
solutions.
3. Defining the level of brighteners and their breakdown products. This will
indicate the need for activated carbon/filtration treatment and the
need for brightener replenishment.
4. The effects of agitation must be carefully noted because they may be relat-
ed to shortcomings of the cell itself.
Cells may also be adapted for other purposes. For example, it need not be nec-
essary to have both a Hull cell and a Haring-Blum cell in regular use, because sev-
eral workers have shown how TP can be measured using the Hull cell by measuring
deposit thickness across the regular panels. In particular, Watson 7 and more

Cathodic ~ ~ Anodic
f
~Dmq41 e m
........ I~d ~ dllml I mliml I~ nlol D................ ~bNdOEEImIN41

,i
M a g n e t i c stirrer

5ram_Ll 1 O0

Fig. 5. Schematic form of the Assaf throwing power ceLL.

mm ~]

516
recently Monev and Dobre 8 have obtained good comparable data.
A cell designed to assess throwing power in small/narrow recesses has been
described by Assaf) and utilizes a rectangular (40 X 40 mm) or round (40 mm diam-
eter = 0.25 dm 8) coupon as cathode placed 5 mm in front of a dummy perspex cath-
ode sheet (see Fig. 5). The anode-cathode spacing is not specified but is typically 150
ram. The throwing power is expressed as the ratio of deposit thickness on the rear
compared to the thickness on the front and as it can be suspended over the
installed agitator it can overcome uncertainties of the effect of agitation. Its use for
assessing solutions for printed circuit board production has been described and its
use in assessing the effects of pulsed current emphasised: throwing power ratios for
pulsed current of 0.66 to 0.75 for DC plating compared to 1 for pulsed currents have
been reported thus demonstrating its sensitivity.10
Aclenowle~nent
This chapter has drawn on some aspects of a similarly titled article by J.B.
Mohler included in earlier editions of the Metal Finishing Guidebook. Readers
requiring more information may care to refer to those volumes.

1. Mohler, J.B., Metal Finishing, 32:55; 1959

2. Skwirzynski, J.K. and M. Huttley, Journal of the ElectrochemicalSociety, 104:650;
1957
3. Gilmont, R. and R.F. Walton, Proceedings of the American Electroplating
Society, 4:239; 1956;Journal of the ElectrochemicalSociety, 103:549; 1956
4. Dimon, 1LA.,Proceedings of the American Electroplating Society, 35:169; 1948
5. Esih, I., Metalloberflache, 20:352; 1966
6. Teraikado, R. and I. Negasaka, Metal Finishing, 77(1):17; 1979
7. Watson, S.A., Transactions of the Institute of Metal Finishing, 37:28; 1960
8. Monev, M. and T. Dobrev, MetalFinishing, 90(10):50; 1992
9. Assaf, Y., Plating, 67(10):12; 1980
10. Gabe, D.R. et al., Plating & Surface Finishing, 88(5): 127; 2001
FurtherReading
Gabe, D.R. and G.D. Wilcox, Transactionsof tbe Institute of Metal Finishing, 71(2):71;
1993
Nohse, W., The Hull Cell, Robert Draper, Teddington, London, 1966
The Canning Handbook, E.F. Spon Ltd., London, 1982, pages 939-943

517