Study on the influence of the additives, metallic contamination and

organic contamination on the stress produced by electrolytic Nickel

bath in plastic line 2 in Radiall Obregn.


Phase 0: Team definition and its roles.

Stablish owner of the project.

The responsible for this study is the Plating Process Engineer Segment 2. He will evaluate the
influence of the additives, organic contamination and metallic contamination in the stress of the
deposit produced by the electrolytic Ni bath in the plastic line 2. If he discovers something
relevant that affects the process he will propose what he considers can improve the process
regarding the blistering problems currently happening in the line.

Phase 1: Problem definition.

Identification of the problem.

Within the process of PPS plastic parts in line 2 there has been a recurrent problem. Some parts
processed in line 2 present at the end of this process blisters on the surface. This blistering
problem affects the aspect and the properties of the parts, making them non compliant. This
problem must be solved in order to improve the effectiveness of the process.

Delimitation of the problem.

The main problem is that pieces processed in line 2 present at the end of the cycle blisters on the
surface.

The scope of this study lies within the plating operations, chemical composition, and other
variables involved in the Nickel plating bath.

Phase 2: Observation.

GLOBAL, Observation of the process.

In Radiall plating lines, the lines that process plastics parts are 2. The process may be divided
for convenience into line 1, and line 2. After line 1 the parts undergo a heat treatment after
which they are processed in line 2. After being processed in line 2 they undergo a second and
final heat treatment after which the are inspected visually and measured its resistivity properties.

STEP by STEP observation.

The process of plating on PPS may be described as:

Surface mechanical preparation.
Set
Cleaning
Etching
Catalizing
Acceleration
1
st
Plating (Electroless Nickel)
2
nd
Plating (Acid Copper)
Dry
Oven

There is a heat treatment after which the process continues as follows:

Cleaning
Neutralizing
3
rd
Plating (Flash Electrolytic Nickel)
4
th
Plating (Electroless Nickel)
5
th
Plating (Electrolytic Nickel)
Dry
Oven

Unmount
Inspection

The accurate tine and flow process can be found in the FIP MEX 5 032 and FIP MEX 5 041.

GLOBAL 2
nd
, Observation of the process.

In this stage I have observed the process and Ive found some things that must be accentuated
because they have influence on the flow of the process and may make it less effective.

The current distribution in the bus bars in the tanks of acid copper and sometimes in the 5
th

plating tank (electrolytic Nickel) is uneven. This affects the current distribution on the pieces
and a result the metal distribution and thickness of the deposit.

Pieces leaving the acid copper tank present localized oxidation that accentuates throughout the
rinses all the way to the oven. As a matter of fact, this oxidation lingers on after the alkaline
cleaner on line 2.

Pieces sometimes spend more time on the rinses when the flow saturates.

Pieces sometimes have no Nickel when leaving the 1
st
electroless Nickel.

There are traces of copper in the anodes and baskets of 5
th
plating tank (Electrolytic Nickel).

Air valves on the 5
th
plating tank (electrolytic Nickel) are often obstructed, causing the air
agitation to be poor.

As a result of a miscalculation on the procedure to analyze chloride ions of electrolytic Nickel
the results given by the laboratory are the double of the actual concentration in the plating tanks.

Recording all information thru the process.

FIP MEX 5 032 and FIP MEX 5 041 establish the chemical composition, operational
conditions, and everything related to the process. FIP MEX 5 102 defines the chemical
composition, operational conditions for the 5
th
plating tank.

My colleagues observed in a study the performed on November 2013 that pieces following the
silver process had a deposit with compressive stress, and pieces following the copper process
had a deposit with compressive stress also. So they formulated a hypothesis for each process:

For the silver process:

This high compressive stress and good adherence could lead the coating to remove the under
layers between electroless nickel and silver due to very low compression of silver that seem to
be very ductile

For the copper process:

The different combination of stress of copper process could explain that plated parts with
copper underlayer are less sensitive to stress and thus to blisters due to the opposite forces that
copper process present vs the electrolytic nickel

Build a clear definition of the problem

To determine if the stress of the deposit is the root cause of blistering in pieces. The stress of the
outer layer (electrolytic Nickel) is evaluated, and at the same time, the influence on the stress of
the deposit due to additives, metallic contamination and organic contamination is evaluated, to
determine what factors could modify the stress and how the stress modifies the blistering
problem.



Phase 3: Investigations.

Investigation of the problem.

Stress.

A residual stress may be defined as a stress within a material which is not subjected to load or
temperature gradients yet remains in internal equilibrium. Residual stresses in coatings can
cause adverse effects on properties. They may be responsible for peeling, tearing, and blistering
of the deposits; they may result in warping or cracking of deposits; they may reduce adhesion,
particularly when parts are formed after plating and may alter properties of plated sheet.
Stressed deposits can be considerably more reactive than the same deposit in an unstressed state.

Two kinds of stress exist in coatings: differential thermal stress and, residual or intrinsic stress
1
.

Depending on the thermal coefficient of expansion of the substrate, the stress induced in the
coating can be either tensile or compressive. Besides differential thermal stress and stress from
the coating process, an added stress can be introduced during use of the plated part. When the
combined tensile stresses exceed the tensile strength of the plating, cracks can develop and these
expose the basis metal to corrosive attack.

Table 1 provides data on the relative magnitude of stresses in electrodeposits. It's interesting to
note that there is an apparent relationship between stress and melting point with the transition
metals exhibiting the highest tensile stresses
2
. Tensile stress (+) causes a plated strip to bend in
the direction of the anode; this type of bending is met when the deposit is distended and tends to
reduce its volume. A plated strip that bends away from the anode is compressively stressed (-);
this type of bending occurs when the deposit is contracted and tends to increase in volume
3
. The
data in Table 1 can be noticeably influenced by additives.




Deposit Melting Point (C) Stress
MPa PSI
Cadmium 321 -3.4 a -20.7 -500 a -3000
Zinc 420 -6.9 a -13.8 -1000 a -2000
Silver 961 13.8 2000
Gold 1063 -3.4 a 10.3 -500 a 1500
Copper 1083 13.8 2000
Nickel 1453 68.9 10000
Cobalt 1495 138 20000
Iron 1537 276 40000
Palladium 1552 413 60000
Chromium 1875 413 60000
Rhodium 1966 689 100000
Table 1. Stress data for some electrodeposited metals
2


Influence of residual stress on fatigue.

Electrodeposits have been known to reduce the fatigue strength of plated parts. The reasons for
this include: 1) hydrogen pickup resulting from the cleaning/plating process, 2) surface tensile
stresses in the deposits, and 3) lower strength of the deposits compared to the basis metal
leading to cracks in the deposit which subsequently propagate through to the base metal.

A general rule of thumb is that tensile stresses in the deposits are deleterious, and the higher the
stress the worse the situation in regards to fatigue strength of the substrate.

How to minimize stress in deposits

There are a variety of steps that can be taken to minimize stress in deposits:

choice of substrate
choice of plating solution
use of additives
use of higher plating temperatures

Influence of Substrate

Typically, with most deposits, there is a high initial stress associated with lattice misfit and with
grain size of the underlying substrate. This is followed by a drop to a steady state value as the
deposit increases in thickness. With most deposits this steady state value occurs in the thickness
regime of 12.5 - 25 pm (0.5 - 1.0 mil). Atomic mismatch between the coating and substrate is a
controlling factor with thin deposits.

A curve showing the relationship of stress in nickel deposited on different copper substrates is
shown in Figure 1. The initial high stress is due to lattice misfit and grain size of the underlying
metal. With fine grained substrates, the maximum stress is higher and occurs very close to the
interface. As the thickness increases the stress decreases to a steady state value, the finer the
substrate grain size, the more rapid this descent
2
. The influence of the substrate on stress is also
shown in Figure 2 which is a plot of stress in electroless nickel coatings on a variety of
substrates (aluminum, titanium, steel, brass and titanium) as a function of phosphorus content.
Besides showing that the substrate has a very distinct influence on stress due to lattice and
coefficient of thermal expansion mismatches, Figure 2 also shows that for each substrate a
deposit with zero stress can be obtained by controlling the amount of phosphorus in the deposit
4
.


Figure 1. Effect of grain size and deposit thickness on tensile stress in nickel deposited from a
sulfamate solution at room temperature
2
.

Figure 2. Stress in electroless nickel as a function of phosphorus content for metals with a high
expansion coefficient (aluminum and brass) and a low expansion coefficient (steel, beryllium
and titanium)
5
.
In terms of adhesion, the ideal case which would provide a true atomic bond between the
deposit and the substrate is that wherein there is epitaxy or isomorphism (continuation of
structure) at the interface. Although this often occurs in the initial stages of deposition, it can
only remain throughout the coating when the atomic parameters of the deposit and the substrate
are approximately the same. Since the stress which develops at the beginning of the deposition
process, is in actuality a measure of bond strength, poor bonding shows up significantly in stress
determinations.
Influence of Plating Solution
The type of anion in the plating solution can leave a marked influence on residual stress as
shown in Table 2 for nickel deposits produced in different solutions. Sulfamate ion provides
nickel deposits with the lowest stress, followed by bromide which also reduces pitting
2
. Not all
plating solutions offer this wide range of anions capable of providing acceptable deposits but
this option should not be ignored when looking for a deposit with low stress.
Nickel Deposit
Solution anion Residual Stress
MPa PSI
Sulfamate 59 8600
Bromide 78 11300
Flouborate 119 17200
Sulfate 159 23100
Chloride 228 33000
Table 2. Influence of anion on residual stress
2
. Deposit thickness was 25!m (1mil), temperature
25C, and current density 323 A/dm
2
. All solutions contained 1M nickel, 0.5M boric acid, pH
was 4 and the substrate was copper.
Influence of Additives
There are numerous additives, particularly organic, which have a marked effect on the stress
produced in deposits.
Small quantities (0.01 to 0.1 g/L) of most sulfur bearing compounds rapidly reduce stress in
nickel deposits. All oxidation states except the plus six oxidation state found in the stable sulfate
provide this effect illustrated in Figure 3. Sulfur in less stable compounds in the plus six
oxidation state, such as aryl sulfonate and saccharin also lower stress compressively
6
. In all
cases where a sulfur compound reduces internal stress compressively, the resulting deposit is
brighter. In fact, the observation that a nickel sulfamate solution is starting to produce a bright
deposit is a good indicator that the anodes are not functioning properly. Polarized or inert
anodes in a nickel sulfamate solution result in formation of azodisulfonate which is an oxidation
product of sulfamate and a major source of stress-reducing sulfur in the deposit
7
. The stress
reducing azodisulfonate can be removed by hydrolysis, on warming, or by a conventional
peroxide carbon treatment
7
. Besides serving as a stress reducer, sulfur in nickel deposits also
exerts a strong influence on notch sensitivity and hardness
8
and can also embrittle deposits at
high temperature
9
.
Contaminants which find their way into plating solutions by accident or because of careless
plating operations can also noticeably influence stress and this should also be kept in mind.


Figure 3. Effects of different forms of sulfur on internal stress in nickel sulfamate deposits
6
.
Influence of Plating Solution Temperature
Increasing the plating solution temperature can reduce stress and this is shown in Table 3 for a
nickel sulfamate solution
10
. Figure 4 visually shows the influence of temperature on stress
comparing nickel sulfamate deposits produced at 15C and 40C. The deposit produced at15C
buckled severely due to its high tensile stress while that produced at 40C showed no
deformation.

Solution temperature (C) Deposit stress
MPa PSI
1.4 410 59500
10.5 186 27000
18 91 13200
25 59 8500
40 17 2500

Table 3. Variation of residual stress with temperature for a nickel sulfamate solution
10
. The
plating current density was 323 A/dm
2

Figure 4. Influence of stress on deposits produced in nickel sulfamate solution at 40C and 15C.
Stress measurement

There are a variety of techniques used to measure stress in deposits and these are well
documented in the literature
3,11,12,13,14
. A listing of stress measurement techniques includes the
following:

- rigid or flexible strip
- spiral contractometer
- stresometer
- X-ray
- strain gauge
- dilatometer
- hole drilling
- holographic interferometry

Rigid or Flexible Strip

This method is based on plating one side of a long, narrow metal strip
11,12,14
. The back side of
the strip is insulated and one end is clamped while the other is free to deflect either during the
plating operation or afterwards (Figure 5). For deposits in tension, the free end deflects towards
the anode, while compressive stress is indicated by deflection of the free end of the strip away
from the anode. If one end of the strip is not constrained during plating, the deflection can be
recorded by attaching, a pointer or a light source which moves over the scale. This allows for
determination of stress as a function of thickness. When the strip is constrained during
deposition, only the final average stress can be determined
11
.

The Stoney formula is used to calculate stress
15
. The variations introduced in this equation over
the years to account for the effects of deposit thickness, modulus of elasticity and temperature
are covered in detail by Weil
11,12
. A strip partially cut into eight sections so that each could
deflect independently of the others has been used in a Hull cell to obtain data on the effect of
current density on stress in one experimental run
16
. Another version of the rigid strip principle is
shown in Figure 6. During plating, opposite sides of a two legged strip are plated and the
resulting deposit causes the strip to spread apart. Deflection is easily measured using the scale
shown in Figure 6
17
.


Figure 5. Flexible strip method for measuring residual stress.


Figure 6. Another version of the flexible strip method for measuring stress.


Spiral Contractometer

This instrument, developed by Brener and Senderoff
18
consists of a strip wound in the shape of
a helix and rigidly anchored at one end (Figure 7). The other end is free to move but as it does it
actuates a pointer on the dial of the instrument. After calibration with a known force, the stress
can be determined from the angle of rotation of the pointer. Compressive residual stress causes
the helical strip to unwind while a tensile stress winds it tighter. Over the years a number of
modifications have been made to the spiral contractometer technique and these are discussed in
detail by Weil
16
.


Figure 7. Brenner and Senderoffs spiral contractometer for measuring stress
18
.

Stresometer

The stresometer (Figure 8) combines Mill's thermometer bulb
19
with the bent strip method. The
deposit is applied on one side of a thin metal disc. Beneath the disc but out of contact with the
plating solution is a metering fluid connected to a precision capillary tube. When a stress
develops in the deposit, the height of the liquid in the capillary tube changes. A tensile stress
causes the disc to "dish in" while compressive stress causes the disc to bulge out. The rise or fall
of the fluid is a direct linear measure of the stress in the deposit
20
.


Figure 8. Kushners stresometer for measuring stress
20
.


X-Ray

Although X-ray diffraction is widely used as a nondestructive method for the determination of
macrostresses, it has found relatively little application for electrodeposits
12
. The method is based
on the changes in spacing between crystal planes associated with macrostresses. The problem is
that it is difficult to determine the involved Bragg angles with sufficient accuracy because the
diffraction lines are broadened, generally because of fine grain size and microstresses.




Strain Gage

This technique provides for real time control of stress and has been used in the electroforming
of optical components
21
. Plating is done on a strain gage simultaneously with the part (Figure 9).
As the plated surface of the gage bends in response to compressive or tensile forces, an analog
output is produced. The strain signals are analyzed by computer programs which vary the output
of the power supply up or down in response to compressive or tensile bending of the plated
surface. Stress control with this method is reported to have been held sufficiently close to zero
so that dimensional accuracy in optical nickel electroforms was 0.15 micrometers (6
millionths)
21
.



Figure 9. Strain gage technique for measuring stress
21
.


Dilatometer

This method relies on the elastic expansion or contraction of a prestressed steel strip brought
about by the force developed along its axis by the tensile or compressive stress in the deposit
applied on its two surfaces (Figure 10). It offers the advantage of a continuous determination
without some of the usual theoretical and practical drawbacks and gives results which compare
well with those obtained by the rigid strip technique
22
.



Figure 10. Dilatometer method for measuring stress
22
.

Hole Drilling

This technique involves drilling a hole in the finished part and measuring the resulting change
of strain in the vicinity of the hole. The method is based on the fact that if a stressed material is
removed from its surroundings, the equilibrium of the surrounding material must readjust its
stress state to attain a new equilibrium. The principle is used quantitatively by drilling a hole
incrementally in the center of strain-gage rosettes and then noting the incremental strain
readjustments around the hole measured by the gages. Unlike most other methods which rely on
independent determination of stress, this method provides data for actual plated parts. It is
particularly useful for parts plated with thick deposits for applications such as joining by plating
or electroforming
23
. Figure 11 is an edge view of an aluminum cylinder plated with thick nickel-
cobalt alloy showing locations of residual stress determinations while Figure 10 shows
maximum principal residual stress versus depth for various sections of the part.


Figure 11. Edge view of plated aluminum cylinder showing locations of residual stress
determinations
23
.


Figure 12. Maximum principal residual stress vs depth for an aluminum
substrate and for two locations plated with Ni-40 Co alloy. See Figure 11
for hole locations.

Holographic Interferometry

Stored beam laser holography has been used to monitor stress in thin films during
electrodeposition
24
. The value of this technique is that it can be applied in situ and is applicable
to very thin films, e.g., less than 20 !m. All the other techniques discussed in this chapter are
typically used for thicker electrodeposits. This technique has practical advantages over
conventional interferometry: it is similarly highly sensitive, can reveal the distribution of stress,
and may be applied to diffusely reflecting surfaces.

Stress theories.

Although a number of theories have been proposed to explain the origins of stress in
electrodeposits, no overall theory that encompasses all situations has been formulated to date.
Buckel
25
theorized that apart from thermal stress there may be as many as six other stress-
producing mechanisms: incorporation of atoms (e.g., residual gases) or chemical reactions,
differences of the lattice spacing of the substrate and the film during epitaxial growth, variation
of the interatomic spacing with the crystal size, recrystallization processes, microscopic voids
and dislocations, and phase transformations. The excellent review articles by Weil
12
detail the
more prominent theories and the following information is excerpted from his publications.


According to Weil, stress theories can be broken down into five categories:

1. Crystalline material growing outward from several nuclei is pulled together upon
meeting.

2. Hydrogen is incorporated in the deposit, and a volume change is assumed when
hydrogen leaves.

3. Foreign species enter the deposit and undergo some alterations thereby causing a
volume change.

4. The excess energy theory assumes that the overpotential is the cause of stress.

5. Lattice defects, particularly dislocations and vacancies, are the cause of stress.

Crystallite Joining.

This theory proposes that crystalline material growing outward from several nuclei is pulled
together upon meeting. For example, the observation of vapor deposition in the electron
microscope led to the discovery of the so-called liquid like behavior. Nuclei growing laterally
were seen to act very similarly to two drops of liquid joining, that is, when they touched they
immediately formed a larger crystal with a shape leaving a minimum surface area. This theory
could explain certain conditions where three dimensional crystallites are nucleated. The
resulting volume decrease to a more dense state would produce a tensile state, however, this
theory does not explain how compressive stresses develop.

Hydrogen.

This assumes that hydrogen is incorporated during deposition and a volume change occurs
when the hydrogen leaves. For example, a layer of deposit contains hydrogen which may form a
hydride with the metal species. Subsequently, the hydrogen diffuses out after the hydride, if
formed, has decomposed causing a decrease in volume. The substrate and deposit beneath the
layer which do not want to contract cause the tensile stress. Compressive stresses result if the
hydrogen, instead of leaving the deposit, diffuses to favored sites and forms gas pockets.

Changes in Foreign Substances.

Alterations in the chemical composition, shape, or orientation of codeposited foreign material
have been postulated to cause the volume change of a plated layer, which originally fitted the
one beneath it. This theory is based on very scant experimental evidence and more data are
needed to support it.

Excess Energy

A metal ion in solution must surmount an energy barrier to be transformed from a hydrated ion
to a metal ion firmly attached to the lattice. This may be thought of as a metal deposition
overvoltage. Once the metal ion is over the hurdle, however, it possesses considerable excess
energy; a group of such ions will have a higher temperature than their surroundings. The
cooling down results in stress. This theory does not explain why compressive stresses are
produced. According to Weil
12
this theory is simply a corollary to such other theories as those
dealing with crystallite joining and dislocations.

Lattice Defects

The mechanical behavior of metals is now known to be determined primarily by lattice defects
called dislocations. Most of the recently developed theories about the origins of internal stresses
in deposited metals have included aspects of dislocation theory or are totally based upon it. Of
these theories, the best developed is one which explains the misfit stresses between a deposit
and a substrate of a different metal when the former continues the structure of the latter (Figure
13). Explanations of the intrinsic stresses in terms of dislocations have been developed
theoretically, but there are not sufficient experimental data to verify them. In spite of this Weil
12

suggests that by a process of elimination, in many instances, the other theories do not apply,
while the dislocation theory can at least explain the observed phenomena in a logical way.



Figure 13. (Top) Edge dislocation forming in an electrodeposited metal
near a surface vacancy in the basis metal. (Bottom) How an array of
negative dislocations produces tensile stress in electrodeposits
2
.



Additives.

Introduction.

The use of additives in aqueous electroplating solutions is extremely important owing mainly to
the interesting and important effects produced on the growth and structure of deposits. The
potential benefits of additives include: brightening the deposit, reducing grain size, reducing the
tendency to tree, increasing the current density range, promoting leveling, changing mechanical
and physical properties, reducing stress and reducing pitting. The striking effects on
electrocrystallization processes of small concentrations of addition agents, ranging from a few
mg/L to a few percent but generally with an effective concentration range of 10
-4
to 10
-2
M,
point to their adsorption on a high energy surface and deposition on growth sites, thereby
producing a poisoning or inhibiting effect on the most active growth sites
26
. In fact, as
Lashmore has pointed out, "electrodeposition is the science of poisoning; one needs to do
something to inhibit the growth of dendrites"
27
. The results obtained with additives seem to be
out of proportion to their concentration in the solution, one added molecule may affect many
thousands of metal ions
26
. Their function and mechanism of interaction is not yet clearly
understood and their investigation so far has been mostly empirical. Nonetheless, plating
additives are extremely important and establishing the proper agents most often determines the
success or failure of a given plating process
28
.

The generic term "plating additives" covers a wide variety of chemicals which affect deposits in
a multitude of ways. The additives can be organic or metallic, ionic or nonionic, and are
adsorbed on the plated surface and often incorporated in the deposit
28
.

Influence on properties.

Table 1 from Safraneks book shows the influence of a variety of additives on tensile strength,
yield strength and elongation in different nickel plating solutions. Tensile strength is shown to
range from 39 to 250 MPa and elongation from 1. 0 to 28 percent, depending on the solution
and additives used.





UTS YS EP





Table 6. Effects of Organic Addition Agents on Strength and Ductility of Nickel Deposits
29

UTS stands for Ultimate Tensile Strenght, YS for Yield Strenght, and EP for Elongation Percent.

Influence on Leveling.

Normal electrodeposition accentuates roughness by putting more deposit on the peaks than in
the valleys of a plated surface since the current density is highest at the peaks because the
electric field strength is greatest in this region. In order to produce a smooth and shiny surface,
more metal has to be deposited in the valleys than on the peaks, which is the opposite of the
normal effect. The function of certain organic compounds is to produce this leveling in plating
solutions. Leveling agents are adsorbed preferentially on the peaks of the substrate and inhibit
deposition. This inhibiting power is destroyed on the surface by a chemical reaction which
releases it, setting up a concentration gradient close to the surface. An example is coumarin
which is used in the deposition of nickel. It adsorbs on depositing nickel by the formation of
two carbon-nickel bonds and inhibits nickel deposition probably by a simple blocking action. It
is removed from the surface and destroyed by reduction with the main product which is
melilotic acid
30
.

Radioactive tracer studies have been particularly effective for studying the behavior of addition
agents. Additives such as sodium allyl sulfonate, labeled by the reaction between allyl bromide
and S labeled sodium sulfite were used in Watts type nickel solutions
31
. Grooved brass cathodes
were plated with nickel. These substrates had been passivated prior to plating so that the foil
could be stripped for counting purposes (Figure 14). Results of the counting experiments (Table
7) show that more activity was deposited on the peaks than in the recesses. Work of this type
supports the theory that the addition agent is preferentially adsorbed on the high points of an
irregular surface where it acts as an insulator. This inhibits deposition of metal and diverts
current to recessed areas
31
. Radioactive tracer techniques, used in Watts nickel solutions, have
revealed that a number of mechanisms are feasible, either diffusion and adsorption, or cathodic
reduction
32
. When two or more compounds were added, the mechanism of incorporation
became more complex. Other work on use of radioactive tracer studies with additives can be
Agent Type of solution PSI PSI
None Fluoborate 74500 52700 16.6
Saccharin, 1g/L Ditto 203000 120000 1
None Sulfamate 80000 50000 8
Naphtalene trisulfonic acid, 8g/L Ditto 140000 110000 1
Naphtalene trisulfonic acid, 8.7g/L +
Coumarin, 1 g/L
Ditto 170000 140000 1
None Sulfamate 110000 70000 7
Naphtalene trisulfonic acid, 8g/L Ditto 150000 110000 1
Dibenzene sulfonic acid, 1.5g/L Sulfamate 75500 - 12
None Sulfate 87500 - -
Trisulfonated naphtalene, 0.02g/L Ditto 250000 - -
Trisulfonated naphtalene, 1g/L Ditto 140000 - -
None Watts 56000 - 28
Nickel benzene sulfonate, 7.5g/L +
triamine tolyphenyl methane chloride,
5-10mg/L
Ditto 212000 - 5
found in references A practical example of the influence of additives on leveling is shown in
Figure 15
33
. A proprietary additive in a copper sulfate solution reduced surface roughness as
much as 70 percent with a deposit as thin as 20 um (0. 8 mil). Besides producing deposits which
level the hills and valleys on a substrate, levelers also inhibit the formation of asperities such as
nodules. This increases the stability of the deposition process, particularly for thick coatings
30
.


Figure 14. Cathode foil and shield for radio tracer studies. Grooved brass cathodes were plated
with nickel which was then passivated to permit stripping of subsequent foils. Counting shield
had grooves that limited betas activating the counter to those from either one peak or one
valley.
31



Figure 15. Leveling power of bright copper deposited in copper sulfate solution containing a
proprietary additive.
33


Foil A Top** Foil B - Top
Peak Recess Peak Recess
125 94 42 27
115 72 33 33
115 53 76 53
143 63 47 81
213 80 177 91
226 163 163 160
224 212 94 97
125 65 147 34
106 64 43 28
55 55 59 45
79 57 58
Foil A - Bottom Foil B - Bottom
Obverse of
peak
Obvserse of recess Obverse of
peak
Obvserse of recess
248 143 145 58
198 103 133 77
152 133 134 84
120 112 154 65
207 102 135 100
254 113 190 128
227 163 212 126
150 146 176 101
146 129 163 82
181 158 144 80
242 129 102
Table 7. Lead Slit Counting Rates for Foils Shown in Figure 14*
*Counting was left to right on the top of the foil and right to left on the bottom, so that the
values in the columns are matched.
**Top refers to the side next to the solution during plating, bottom to the side next to the
cathode.
31


Influence on brightening.

A bright deposit is one that has a high degree of specular reflection (e.g., a mirror), in the as-
plated condition. Although brightening and leveling are closely related, many solutions capable
of producing bright deposits have no leveling ability
34
. If the substrate is bright prior to plating,
almost any deposit plated on it will be bright if it is thin enough. However, a truly bright deposit
will be bright over a matte substrate and it will remain bright even when it is thick enough to
hide the substrate completely. Plating solutions without addition agents seldom or never
produce bright deposits. There is a direct relationship between brightness and surface structure
of electrodeposits as shown in Figure 16
35
. The measure of smoothness used in this example is
the fraction of the surface area which does not deviate from a plane by more than 0.15 !m,
which is of the order of the wavelength of visible light. This value was chosen because it has
been found that with specularly bright nickel, there are no hills higher or valleys deeper than
0.15 !m
35,36


Figure 16. Relationship between quantity of reflected light (brightness) and fraction of area with
roughness less than 0.15!m
36


Classification and types of additives.

Additives can be classified into four major categories: 1-grain refiners, 2-dendrite and
roughness inhibitors, 3-leveling agents, and 4-wetting agents or surfactants
28
. Typical grain
refiners are cobalt or nickel codeposited in trace amounts in gold deposits. Dendrite and
roughness inhibitors adsorb on the surface and cover it with a thin layer which serves to inhibit
the growth of dendrite precursors. This category includes both organic and inorganic materials
with the latter typically being more stable. Leveling agents, such as coumarin or butynediol in
nickel solutions, improve the throwing power of the plating solution mostly by increasing the
slope of the activation potential curve. The prevention of pits or pores in the deposit is the main
purpose of wetting agents or surfactants
28
.

Metals differ in their susceptibility to the effect of additives, and the order of this susceptibility
is roughly the same as the order of their melting points, hardness and strength; it increases in the
order Pb, Sn, Ag, Cd, Zn, Cu, Fe, Ni
37
.
Thousands of compounds are known that brighten nickel deposits from the sulfate-chloride
solution, while it is only fairly recently that ways of brightening tin deposits from acid solutions
have been developed. The progression in the series corresponds to: 1) the increasing tendency of
metal ions to form complexes and 2) to increasing activation polarization from simple ions. This
is in the reverse order to the overvoltages observed in the evolution of hydrogen on metal
cathodes. Lyons suggests that: "An atom which is capable of interacting strongly with other
atoms of the same or other kinds tends to form a strong crystal lattice with a relatively high
melting point, to coordinate strongly with ligands, to decoordinate water slowly, and to catalyze
conversion of atomic to molecular hydrogen"
37
.

Additives are often high molecular weight organic compounds or colloids since small ions or
molecules are generally not very effective
38
. This is shown in Table 8 which relates minimum
concentration of organic compounds required to impart appreciable brightness to nickel
deposits
39
. The size of the molecule can also influence the stress in the deposit. Coumarin,
which is a small molecule compared to phenosafranine (Figure 17) reduces macrostress in
nickel deposits, whereas, phenosafranine increases tensile macrostress
40
.

An open discussion of the components of brightener systems is difficult because many of these
systems are proprietary. Suppliers guard their formulations from distribution simply because the
brightener market is so competitive. However, there are numerous technical publications
detailing many of the additives commonly used. A listing of the materials that have been used
as additives in plating solutions culled from the open literature would be monumental and will
not be attempted here. However, some limited examples will be presented in the material that
follows.

!"#$ &' (&)#*+, -./)#0$ 1234 56+4 7&+(4 !& 8963:;$+ <$#&=6; >)?@?A
B$9" 0/93$ 5/3$+;/ ,"$ C4CCCCDE
F6("(06( G/((:/96+ C4CCCHD
5&+&("(06( I*;*9/0 C4CCH
G:&9; (:/6+ /0J"0 (&)#*+,= 1(9"&+6;960$ C4CCK
Table 8. Relationship Between Molecular Size and Minimum Concentration of Organic
Compound Required to Cause Brightening in Nickel Plating
39


Nickel - The key to modern bright nickel plating was the discovery of combining an organic
"carrier" brightener with an auxiliary compound to produce brightness and leveling
41
. These are
referred to as Class 1 and Class I1 brighteners and materials of each type are listed in Table 9.
Brighteners of the first class have two functions: 1-provide bright deposits over a bright
substrate and 2-permit the second class brighteners to be present over an acceptably wide range
of concentrations. Brighteners of the second class are used to build mirror-like lustre. However,
most of these lead to excessive brittleness and stress in deposits in the absence of brighteners of
the first class
42
. Comparisons of the two brightener classes are provided in Table 10. For more
detail on nickel plating brighteners, see references
39, 41, 42, 43, 44, 45, 46



Table 9. Brighteners for Nickel
42


Carriers (Class I) Brighteners (Class II)
Bright or cloudy deposits, unable to provide high lustre with
continued plating.
Brilliant leveling and increasing lustre.
Sulfur (0.03%) occluded in deposit when Class I compunds
are used without Class II compounds.
Introduces carbon in the deposit.
No critical upper concentration, used in high concentrations
(1-10g/L). Cathode potential increases 15-45mV in low
concentrations, then very little change with further additions.
Cathode potential continues to increase
sharply with increases in concentration.
Do not cause crack or peeling. Deposits crack and peel when the
cathode potentail increase exceeds
approximately 30mV.
Reduce stress, can result in compressive stress. Lessen
ductility slightly.
Have a very deleterious effect on
properties, producing brittle, highly
stressed deposits.
Table 10. Comparison of Carriers and Brighteners Used in Nickel Plating Solutions
39, 46

Mechanisms.

Additives act as grain refiners and levelers because of their effects on:
1. electrode kinetics and
2. the structure of the electrical double layer at the plating surface.
Since additives are typically present in extremely under diffusion control and, therefore, quite
sensitive to flow variations. The effects of additives are often manifested by changes in the
polarization characteristics of the cathode. Many are thought to function by adsorption on the
substrate or by forming complexes with the metal. This results in development of a cathodic
overpotential which is maintained at a level which allows the production of smooth, non-
dendritic plates having the desired grain structure
47
. An example is bright nickel deposition
which is accompanied by a cathode potential increase (polarization) of the order of 20 mv, or
more as shown in Figure 18
39
.


Figure 18. Cathode potential-concentration curve for 1-naphtylamine-4,8-disulfonic acid. The
first sign of brightening of nickel deposit is indicated by an arrow
39
.

Numerous mechanisms have been suggested to explain behavior of additives:
1. blocking the surface,
2. changes in Helmholtz potential,
3. complex formation including induced adsorption and ion bridging,
4. ion pairing,
5. changes in interfacial tension and filming of the electrode,
6. hydrogen evolution effects,
7. hydrogen absorption,
8. anomalous codeposition, and
9. the effect on intermediates.
These are discussed in detail in a comprehensive review by Franklin
48
. Additional excellent
coverage on mechanisms of levelling and brightening of addition agents can be found in the
paper by Oniciu and Muresan
49


Decomposition of addition agents.

Addition agents are generally consumed in the deposition process. For example, in the case of
nickel they may be decomposed and the products in part incorporated in the deposit (sulfur,
carbon, or both) or released back into the electrolyte. At a pH of 4, approximately 90% of the
coumarin consumed at the cathode is reduced to melilotic acid and incorporated in the deposit
43
.
Radiotracer work has shown virtually complete molecules of melilotic acid, of approximately
lOA incorporated in nickel deposits plated from solutions containing coumarin
32
. Figure 19
relates labeled sulfur content of a nickel deposit to concentration of saccharin in the solution
and is similar in shape to that obtained with carbon when coumarin is used in nickel solutions.
Breakdown products of additives can affect internal stress in the deposit. For example, eight
decomposition products are possible with saccharin (benzoic acid sulfimide) and these are listed
in Figure 20. Of these eight products, it has been shown that o-toluene sulfonamide and
benzamide are found in Watts nickel solutions when saccharin is used
50
. Figure 21 shows the
build up of these two decomposition products as a function of solution electrolysis time and
their influence on stress in the deposit. In the case of these products, when their concentration
gets too high, they are removed by treatment with activated carbon.


Figure 19. Relationship between bulk concentration of saccharin in a Watts nickel plating
solution and sulfur content of deposit. Plating conditions: temperature 55C, pH= 4.4 and
current density 4 A/dm
2

43
.


Figure 20: Possibilities for the decomposition of benzoic acid sulfimide (saccharin).
50


Figure 21: Decomposition of benzoic acid sulfimide (saccharin) during electrolysis and its
influence on stress.
50


Control and analysis of additives.

Lack of control of plating solutions is a major problem which leads to reduced reliability and
increased costs for plated parts. One reason that progress in this area has been slow is the
difficulty of performing quantitative analysis on the additives, often a mixture of two or more
compounds (not to mention the numerous additive breakdown products that can accrue with
time) in the ppm and ppb ranges in the presence of high concentrations of electrolytes
51
.
Techniques that are available include the Hull cell, bent cathode, chromatography, a variety of
electroanalytical methods, impedance probes and spectrophotometry.

Hull Cell.

A number of researchers have stated that the Hull Cell has probably contributed more to the
advancement of electroplating than any other tool
52,53
and this is likely true. Jackson and
Swalheim contend that "a plater without a Hull Cell is like an electrician without a voltmeter"
54
.
It is a simple, easy test to run and does not require advanced technical training for
interpretation of results. With this test one can determine plating characteristics over at least a
tenfold change in current density range. Although it is not nearly as exotic and complex as
many of the other analytical tools discussed in this section the fact that this tool, first
demonstrated in 1939
55
is still viable shows that it has weathered the test of time
56
.

The Hull Cell is a trapezoidal box of non-conducting material with one side at a 37.5 degree
angle (Figure 22). An anode is laid against the right angle side and a cathode panel is laid
against the sloping side. When a current is passed through the solution sample contained in the
cell, the current density along the sloping cathode varies in a known manner. In this way the
character of the deposit at a range of current densities is determined in one experiment. Current
used in the cell varies from 1 to 3 amps, and time from 2 to 10 minutes, depending on the type
of solution being tested. Special rulers or scales are available that are marked to show specific
current densities on a plated Hull Cell panel depending on the amperage used
56
(Figure 23). The
standard Hull Cell is 267 ml capacity, a volume selected in premetric days because 2 grams of
material added to the cell corresponds to a 1.0 oz/gal addition to the main plating solution.
Today Hull Cells are available in a variety of sizes including 500 ml and 1 liter to fulfill needs
of those working in the metric system.


Figure 22. Hull Cell: a) top view, b) plan view of 267 mL cell.


Figure 23: Hull cell ruler
56
. Not to scale. Only for illustrating purposes.

Figure 24: Code defining the surface appearance of a Hull cell panel
57
.


Figure 25: Gornall cell for studying surface to hole ratios for printed wiring boards
59
.

A Hull cell panel gives more information than the useful plating range. It reveals a pattern of
bright, semi-bright, dull, burned, pitted and cracked areas that typically describe results of a
specific test. Figure 24 shows one technique for recording data from Hull Cell panels
57
.


Modifications to the Hull Cell have appeared including a cell with holes in the two parallel sides
to permit solution circulation while the cell is immersed in the actual plating tank under
evaluation
58
. This cell can be operated for long periods of time without temperature fluctuation.
A more recent modification is the Gomall Cell (Figure 25) which is used for testing solutions
for the printed wiring board industry
59
. This version allows for plating of samples with drilled
holes and provides accurate surface-to-hole ratios as a function of current density. For more
detail on the Hull Cell and its operation besides the references already cited, the book by
Nohse
60
is recommended.

However, while the Hull Cell has been adequate in the past, the increasing demand for process
automation and the increasing complexity of parts makes the need for quantitative control of
organic additives more important. The Hull Cell can be misleading when used to evaluate high
speed processes because parameters related to solution flow, solution geometry and current
distribution are not always reproduced
61
. Also, new additives required for high current density
operation and other advances will have to function under much more severe constraints than
those presently in use and will require more sophisticated control than attainable with the Hull
Cell.


Bent cathode.

Another test that can be used to monitor some additives is the bent cathode. Shown in Figure 26,
a panel bent in this configuration and plated in either a beaker in the laboratory or in the actual
production tank can provide information on leveling, burning and striations, roughness, low
current density problems and pitting. Inspection is performed after opening the bottom portion
of the panel
62



Figure 26. Bent cathode test panel
62
.

Chromatography.

Chromatographic techniques have been finding increased usage in monitoring of plating
solutions
63
. Their main attraction is the ability to quantitate simultaneously low concentrations
of several inorganic and organic solution constituents in one analytical run. With
chromatography, the usage of two terms-High Performance Liquid Chromatography (HPLC)
and Ion Chromatography (IC) has caused some confusion. For this reason a more general term,
Liquid Chromatography (LC) is now preferred
63
. A detailed explanation of modern LC methods
can be found in reference
64
and applications of LC for analysis of electroplating additives in
Table 11. Liquid chromatography is shown schematically in Figure 27. It consists of four
modes:

1. a sample delivery mode - this includes a high-pressure analytical pump and a sample
injection valve;
2. a separation mode - this includes one of a variety of analytical separator columns;
3. a detection mode - this includes one of a variety of detectors; and
4. a data reduction mode - this can range from a simple X-Y strip chart recorder to a
personal computer system
65
.




Table 11. Plating Solution Additives Analyzed by Various Techniques.


Figure 27. Schematic of an HPLC system
65
.

As shown in Table 11, chromatographic techniques have been used to analyze additives in acid
copper, nickel, tin, tin-lead and zinc plating solutions. Figure 28 shows an HPLC chromatogram
of some organic brighteners cited in the literature for zinc plating
66
. The breakdown products of
saccharin discussed earlier and shown in Figures 20 and 21 were determined by
chromatography. A recent innovation includes the use of scanning UV detectors in the
chromatographic system. Unlike conventional single wavelength two dimensional
chromatograms, the recordings produced by scanning detectors are three dimensional. These 3
D chromatographic plots facilitate the identification of unknown peaks and help to improve
knowledge of chemical reactions responsible for the properties of deposits. Figures 29 and 30
show respectively a conventional chromatogram and the corresponding 3-D plot obtained. The
peaks 1,2,3 and 4 came from one additive solution and the two late eluting peaks 5 and 6 were
attributed to a replenisher solution. Peak 2 originating from the replenisher additive could be
identified as phenol which was a degradation product from the organic additive
67
.


Figure 28. HPLC chromatogram of some organic brighteners cited in the literature for zinc
plating
66
.


Figure 29. Single wavelength (210 nm) chromatogram of a tin plating solution
67
.


Figure 30. Three dimensional chromatographic plot of a tin plating solution
67
.


Electroanalytical techniques.

Dramatic progress has been made in recent years in electroanalytical methodology, particularly
in the areas of polarography, voltammetry and impedance measurements
51,68
. Heavy emphasis is
increasingly being placed on use of electroanalytical approaches for addressing surface finishing
issues, both on the level of fundamental investigations and the control of practical processes.
This use of electroanalytical techniques to provide process control of plating solutions is a
natural continuation of the methods and technology familiar in any plating shop since the basic
principles governing electroplating on a metal substrate and electron transfer at an electrode are
die same
68
. In each of these situations important items include polarization, current efficiency
and iR drop.

Techniques that are being used include dc and ac polarography, differential pulse polarography,
square wave voltammetry, linear sweep and cyclic voltammetry, ac cyclic voltammetry and
impedance measurements. They will be reviewed briefly in the following pages; for more detail
the excellent reviews by Okinaka aid Rodgers are recommended
51,68
. Table 11 provides
examples of use of these techniques for analyzing additives in plating solutions while Table 12
describes the techniques and provides some comparisons. Most of the interest has focused
primarily on polarography and voltammetry
68
. Both refer to the measurement of a current
response to an applied potential. This potential changes with time according to a known
function similar to a staircase ramp or pulse.

A. Polarography.

A typical instrument for active (analytes in solution are oxidized or reduced by means of an
applied potential) electroanalytical techniques is shown in Figure 31
68
. With polarography, a
dropping mercury electrode (dme) is used to present a fresh, reproducible surface (Figure 32).

A major improvement to the original dc polarographic method is differential pulse polarography.
With this approach, a small amplitude pulse is superimposed on the dc ramp and timed to occur
near the end of the lifetime of each mercury drop (Figure 33). With this technique it is possible
to obtain enhancement of the detection limit by a factor of at least 100 times as compared to dc
polarography
51
. To illustrate this sensitivity, differential pulse polarograms of o-
chlorobenzaldehyde used as a brightening agent in a chloride zinc solution are shown in Figure
34. This compound has been determined at concentrations as low as 0.1 ppm
51,69
.



Table 12. Comparison of Various Electroanalytical Methods
51
.


Figure 31. Schematic of typical instrument for active electroanalytical techniques
68
.


Figure 32. DC polarography
68
.


Figure 33. Differential pulse polarography
68
.



Figure 34. Differential pulse polarograms of o-chlorobenzaldehyde in a chloride zinc plating
solution in supporting electrolyte containing 0.6M acetate buffer (pH=5) and 0.04M EDTA
69
.

B. Cyclic Voltammetry Stripping

Cyclic voltammetry stripping (CVS) is perhaps the most widely used electroanalytical method
for studying electrode processes
51
. Tench and Ogden and their circle of researchers have
pioneered in the use of CVS, particularly for controlling copper pyrophosphate solutions for
printed wiring board production. Their work is detailed in references
70,71,72,73,74,75,76,77,78,79,80,81,82

and the following is excerpted from their reports. With CVS, the concentration of brightening or
leveling additives in the plating solution is determined from the effect these additives have on
the electrodeposition rate
70
. The potential of an inert electrode immersed in the solution is
cycled as a function of time. As a result of this, a small amount of copper is alternately
deposited on the electrode and stripped off by anodic dissolution. A reproducible concentration
of brightener is maintained by rotation of the electrode. The technique is illustrated in Figure 35
which shows steady-state voltammetry curves for a Pt disc electrode rotated at 2500 rpm and
swept continuously at 50 mV/sec between 0.700 and 1 V vs. SCE (saturated calomel electrode)
in a pyrophosphate solution containing 1 and 2 ml/l of proprietary brightener
70
. Copper
deposition occurs between -0.3 and -0.7 V for both sweep directions while the copper deposit is
stripped on the anodic sweep between -0.3 and -0.05 V. The area under the stripping peak can
be related to the concentration of brightener in the solution since it corresponds to the charge
required to oxidize the copper deposit and is proportional to the average deposition rate for that
cycle
70
. A comparison of the peak areas for solutions containing 1.0 and 2.0 ml/l of proprietary
brightener (Figure 35) reveals that the brightener has a strong decelerating effect on the rate of
copper deposition. Figure 36 shows that the stripping peak without rotation (Ar) is much larger
than that with agitation since the brightener concentration at the electrode surface is nearly zero.
This ratio is an effective measure of brightener concentration
70
.


Figure 35. Cyclic voltammograms at 50mV/sec for rotating Pt disc electrode in a copper
pyrophosphate solution at 22C
70
.


Figure 36. Cyclic voltammograms with and without rotation at 50mC/sec for a Pt disc electrode
in a copper pyrophosphate solution at 22 C
70
.

A few examples showing the values of CVS for production control are presented in Figures 37
and 38. One factor that should be taken into account in controlling copper pyrophosphate
solutions is the variation of the strength of the additive from batch to batch. Figure 37 shows
plots of the CVS rate parameter (Ar/As) for three different batches of additive. Significant
differences in both the overall concentration of the active additive and the balance between
monomer and dimer are evident. Effective concentration of different batches of additives has
been shown to vary by as much as a factor of three
77
.

Application of CVS to production copper pyrophosphate solutions reveals considerable
information not only about additive behavior but also about the overall functioning of the
solution. This is illustrated in Figure 38 which shows voltammograms obtained with the
electrode rotation (2500 rpm) in various production solutions
77
. Clearly, the CVS method also
provides a "fingerprint" that reflects the overall functioning of the solution and in some cases
yields specific valuable information.


Figura 37. Plot of Ar/As as function of the concentration of three batches of additive for a
copper pyrophosphate solution
77
.


Figure 38. Cyclic voltammograms at 50 mV/s for a rotating Pt disc electrode (2500 rpm) in
various production copper pyrophosphate solutions at 22C
77
.

Solution Composition Stripping Peak
a. New solution formulated to
manufacturers specifications
Well defined stripping peak and very little current at
more anodic potentials
b. Accelerated additive
concentrations
Stripping peak is much sharper
c. Excessive additive levels Stripping peak is strongly suppressed
d. Organic contaminants Current wave produced at more anodic potentials
reflects solution contamination level
e. Residual hydrogen peroxide This distorted voltammogram reflects residual hydrogen
peroxide lingering in solution after treatment with
hydrogen peroxide and carbon to remove organics
f. High solution pH This produces a splitting of the stripping peak

Another example of the value of CVS for monitoring solution contaminants evolved
around defective carbon filter cartridges
77
. CVS analysis of a carbon treated solution indicated
high amounts of contaminants even when the purification procedure was repeated with a
fresh filter cartridge. This led to the discovery that the filter supplier had changed
manufacturers and detrimental contaminants were being leached into the solution from the
sizing material in the new cartridges. Without CVS to detect this problem, many circuit boards
would have been rejected.

Originally developed for pyrophosphate solutions, cyclic voltammetry stripping is now
being used for other plating solutions as well (Table 11). However, with acid copper
solutions, CVS has two drawbacks:

1. heavily adsorbed films from some acid copper additives undergo successive
oxidation/reduction reactions during each analysis cycle and interfere with the
copper stripping peak, and

2. most acid copper plating solutions "age" during operation by forming byproducts
and this invalidates use of a standard curve of stripping vs. additive concentration
generated for a fresh solution
83
.

Realizing these difficulties, Tench and White modified the analysis technique to step the
electrode potential over a range to include plating, stripping, cleaning and equilibration
82
.
This technique, called cyclic pulse voltammetric stripping (CPVS), minimizes the effects of
contaminants.

C. Impedance Techniques

An electrochemical impedance probe has been developed for monitoring organic plating
solution additives
84,85
. With this method it is possible to measure increases in interfacial
resistance on the surface of a noble metal working electrode and then calibrate in terms of
additive concentration. Additives analyzed via this technique are listed in Table 11.

D. Spectrophotometry

Spectrophotometric methods that take advantage of the ultraviolet light absorbance exhibited by
many brighteners have been used for determining the concentrations of brighteners in copper
66

and nickel
86
.

Internal Stress

Internal stress refers to forces created within the deposit as a result of the electrocrystallization
process and/or the codeposition of impurities such as hydrogen, sulfur and other elements
87
.
Internal stress is either tensile (contractile) or compressive (expansive) in nature. In tensively
stressed deposit, the average distance between nickel atoms in the lattice is greater than the
equilibrium value, creating a force that trends to drive the atoms closer together. When a
tensively stressed deposit is detached from its substrate, it contracts. In addition, if a thin
cathode strip is electroplated on one side only (by painting the back and placing the bare side
facing the anode), a deposit stressed in tension will cause the strip to band or curl toward the
anode. In compressively stressed deposits, the atoms are closer together and the force tends to
drive them further apart. When detached from the substrate compressively stressed deposits
expand and a thin strip plated on one side, as described, will bend away from the anode.
Dislocation theory provides a logical explanation of the origins of internal stress in
electrodeposits
12,88

Stress in electrodeposited nickel can vary over a wide range depending on solution composition
and operating conditions. In general, nickel electrodeposited from additive-free Watts solutions
exhibits a tensile stress within the range of 0-55 MPa. Compressively stressed nickel deposits
are obtained from solutions that contain sulfur-containing organic additives similar to the
carriers that are added to bright nickel plating solutions. As far as is known, compressively
stressed nickel deposits are almost always associated with the codeposition of sulfur.

Additives.

Carriers (Brighteners of the First Class, Secondary Brighteners, Control Agents)

These are usually aromatic organic compounds. Examples are benzene sulfonic acid, 1,3,6-
naphthalene sulfonic acid (sodium salt), p-toluene sufonamide, saccharin (o-benzoic
sulfonimide), thiophen- 2 sulfonic acid, benzene sulfinic acid, and allyl sulfonic acid. Carriers
are the principal source of the sulfur codeposited with the nickel. Their main function is to
refine grain size and provide deposits with increased luster compared with matte or dull deposits
from baths without additives. When used by themselves, carriers do not produce mirror-bright
deposits. Carriers are used in concentrations of about 1 25 gL
-1
, the exact concentration
depending on the specific compound. Carriers are not consumed rapidly by electrolysis, and
consumption is primarily by dragout and by losses during activated carbon treatments. The
stress reducing property of carriers is increased if they contain amido or imido nitrogen. For
example, saccharin is a most effective stress reducer and often helps to decrease or eliminate
hazes.


Brighteners (Brigkteners of the Second Class, Primary Brighteners, Leveling Agents)

In combination with carriers and auxiliary brighteners, brighteners produce brilliant deposits
having good ductility and leveling characteristics over a wide range of current densities. Some
of these compounds include formaldehyde chloral hydrate, o-sulfobenzaldehyde, allyl sulfonic
acid, coumarin; o-hydroxy cinnamic acid, diethyl maleate, 2-butyne-l,4-diol; 2-butyne-l,4-
disulfonic acid; ethyl cyanohydrin, p-amino azo benzene, thiourea,and allyl
thioureaandpolyethylene glycols of various kinds. The best-known example in this class may be
coumarin (1,2-benzopyrone), the leveling agent introduced by DuRose for producing semibright
nickel deposits. Because they increase the internal stress and promote brittleness of nickel
deposits, brightener concentrations are kept low and carefully controlled. Concentrations of
0.0050.2 gL
-1
are generally used. The rates of consumption of these materials may vary within
wide limits.

Auxiliary Brighteners

Auxiliary brighteners augment the luster attainable with carriers and brighteners and increase
the rate of brightening and leveling. Some examples are sodium allyl sulfonate; zinc, cobalt,
cadmium; and 1,4-butyne 2-diol. The concentration of these additives may vary from about 0.1
to 4 gL
-1
Sulfobetaines, such as pyridinium propyl sulfonate, are especially active sulfur
containing organic compounds that have a powerful effect on leveling in nickel deposits.
However, because they introduce sulfur into the deposit, they cannot be used for semibright
nickel plating. They can be especially effective when added to bright nickel plating solutions in
low, carefully controlled concentrations. The inorganic metallic ions -zinc cobalt, cadmium- are
not often used anymore as auxiliary brighteners.


Electrocrystallization.

The mechanism of nickel electrodeposition involves surface adsorption of species formed in the
cathode film accompanied by inhibition of growth of certain crystal faces. In the absence of
organic additives, species like H
2
, H
ads
, and Ni(OH)
2
, which form as a result of the reduction of
hydrogen ions, determine most of the microstructural features of the nickel deposit
89,90
. The
mechanism by which unsaturated organic additives modify the electrocrystallization process to
yield mirrorbright surfaces also involves adsorption, hydrogenation, and desorption. The
organic molecule is adsorbed on the surface via the unsaturated bond, blocking certain sites on
the nickel lattice and thus altering the growth rates of different crystal faces. The unsaturated
bond reacts with hydrogen in the cathode film and the resulting reduction products are desorbed
from the surface and/or incorporated into the deposit. The rates of those processes are
influenced by the degree of unsaturation, the size and shape of the organic molecule, the
functional groups present, aromatic rings, and other stereochemical factors. That general
mechanism has been confirmed and clarified by studying the effects of individual additives
91
.
For example, the active group in a carrier like sodium benzene sulfonate is =C-S.
Hydrogenolysis of the =C-S bonds results in the formation of sulfur anions that are adsorbed on
the (110) crystallization direction causing the [100] texture to predominate. The sulfur is
incorporated into the deposit as the sulfide. Below 25 Adm
-2
the active groups in saccharin,
=C-S and S=O, react with hydrogen to form sulfur anions that are also codeposited and suppress
growth in the (110) direction, promoting the formation of the [100] texture and extending the
[100] planes in the surface of the deposits, but above that current density, hydrogenation of
adsorbed C=C and C"C bonds also takes place. This promotes reduction of hydrogen ions and
increases the pH in the cathode film with the consequent formation of a colloidal suspension of
nickel hydroxide. The selective adsorption of colloidal nickel hydroxide inhibits growth in the
(100) direction, favoring formation of [211], [211] + [111], and [111] textures. The active
groups in sulfur-free brighteners include C=C, C"C, C"N, and others, and the mechanism by
which these modify crystal growth also involves hydrogenation, increased alkalinity in the
cathode film, and precipitation and inhibition of crystal growth by colloidal nickel hydroxide
causing [211] and [111] textures to dominate crystallographic features. The two mechanisms by
which sulfur-containing and sulfur-free organic addition agents influence crystal growth are
thus distinctly different, and complex sulfur-containing compounds like saccharin apparently
display features of both. The effect of pulsed reversed current in the presence of organic
additives has also been studied
92
. Brightness is attained if the microstructural components of the
surface form a plane from which they do not vary by distances greater than the wavelength of
light
93
. The criterion for brightness is thus not simply the production of fine-grained deposits but
the creation of flat crystals. Exactly how a complex mixture of carriers, brighteners, and
auxiliary brighteners act in concert to meet those criteria may need further elucidation, but the
synergistic effects first described in the classical work of Edwards are probably involved
94
.


Effects of Codeposited Sulfur

The incorporation of sulfur has several important effects. Sulfur increases the electrochemical
reactivity of bright nickel compared to sulfur-free nickel, and that effect is applied in multilayer
coatings to improve corrosion performance. Codeposition of sulfur changes the intrinsic internal
stress of electrodeposited nickel from tensile (contractile) to compressive (expansive) and the
incorporation of sulfide, an anion considerably larger than the nickel atom, must compress the
nickel atoms in the crystal lattice. Carriers are thus useful for controlling internal stress. In
addition, sulfur increases the hardness and lowers the elongation percentage of electrodeposited
nickel.




Deposit Properties

The main constituents in Watts solutions affect the properties of electrodeposited nickel. Nickel
sulfate improves conductivity and metal distribution and determines the limiting cathode current
density for producing sound nickel deposits. Nickel chloride improves anode corrosion but also
increases conductivity, throwing power, and uniformity of coating thickness distribution. In
addition chlorides increase the internal stress of the deposits, and they tend to refine grain size
and minimize formation of nodules and trees. Boric acid is added for buffering purposes and
affects the appearance of the deposits. Deposits may be cracked and burnt at low boric acid
concentrations. Anionic wetting agents or surfactants that lower the surface tension of the
plating solution so that air and hydrogen bubbles do not cling to the parts being plated are
almost always added to control pitting and, by eliminating porosity, have an indirect effect on
corrosion performance.

Operating conditions, such as pH, temperature, current density and chloride content, affect the
properties of deposits from Watts solutions
95
. In a Watts solution, hardness, tensile strength, and
internal stress increase above pH 5.0 while the elongation percentage decreases as shown in (Fig
39). The hardness increases rapidly at low values of current density (Fig. 40). Increasing the
temperature of the plating solution causes hardness and tensile strength to reach minimum
values at about 55C, while the elongation percentage is a maximum at that temperature (Fig
41) Increasing the chloride ion concentration affects the properties of deposits from Watts
solutions; for example, the elongation percentage is at a maximum, and hardness and tensile
strength are at minimum values when the solution contains 25% by weight nickel chloride (Fig
42). In general, conditions that increase the hardness of a nickel deposit will increase its tensile
strength and lower its ductility. Close control of the main constituents and the operating
conditions is thus required to produce nickel electrodeposits with consistent and known
properties.

The properties of deposits from Watts and sulfamate solutions are affected in different ways by
changes in operating conditions, as illustrated qualitatively in (Fig 43)
96
, For example, internal
stress is not significantly affected by increasing the temperature of a Watts bath, whereas
increasing the temperature in a sulfamate solution reduces internal stress significantly. Cathode
current density has a relatively small effect on the tensile strength of deposits from a Watts
solution, but increasing current density reduces the tensile strength of deposits from a sulfamate
solution.

The mechanical properties measured at temperatures from -195C to 870C of nickel
electrodeposited from Watts, sulfamate, and all-chloride solutions were determined and
compared to the properties of wrought nickel by Knapp and Sample
97
(Fig 44). At -195C,
chloride and sulfamate nickel had ultimate tensile strength in excess of 100 kg mm
-2
compared
to a value of 56 kg mm
-2
for Watts and annealed wrought nickel. The reduction in the
elongation percentage above 450C for the three types of electrodeposited nickel was attributed
to the presence of small amounts of sulfur in the electrodeposited nickel. Although wrought
nickel has comparable levels of sulfur, it also contains small amounts of manganese that prevent
sulfur from migrating to grain boundaries at elevated temperatures where it forms nickel sulfide,
which reduces high-temperature ductility. The codeposition of small amounts of manganese
with nickel has since been shown to improve high-temperature ductility
98
. Considerable
information on the physical and mechanical properties of electrodeposited nickel, nickel alloys,
and nickel composite coatings is available
99,88
.


Figure 40. Influence of pH on the internal stress, tensile strength, ductility and hardness of
nickel electrodeposited from a Watts solution at 55C and 5 A dm
-2

95
.


Figure 41. Influence of current density on the internal stress and hardness of nickel
electrodeposited from a Watts solution at 55C and pH 3.0
95
.


Figure 42. Influence of temperature on the elongation, tensile strength and hardness of nickel
electrodeposited from a Watts solution at pH 3.0 and 5 A dm
-2

95
.


Figure 43. Influence of chloride concentration on the elongation, internal stress, hardness and
tensile strength of nickel electrodeposited from Watts type solutions at pH 3.0, 55C and 5 A
dm
-2

95
.


Figure 44. Qualitative effects of operating conditions on the properties of Nickel
electrodeposited from Watts and sulfamate solutions.

Internal Stress Measurements.

There are many ways that the internal stress of electrodeposits can be measured, but the one
most frequently applied in production is the spiral contractometer method (ASTM standard B
636
100
). The method is based on electrodepositing nickel on the outside of a helix formed by
winding a strip of metal around a cylinder followed by annealing. During the measurement of
stress, one end of the helix is fixed in the contractometer and the free end is attached to an
indicating needle that moves as stress develops. Internal stress can be calculated from the degree
of needle deflection on the circular dial. Contractometers and precoated helices to prevent
internal electroplating are commercially available. Modifications of the contractometer method,
including measuring the needle deflection electronically, have been made
11
. Rigid and flexible
strip methods are alternative techniques that give reliable results
101
. The strain gage method
permits stress to be monitored and controlled throughout the electrodeposition process, and the
method has been applied in the production of electroformed optical parts having dimensional
accuracies of 0.15 mm
102
. The dilatometer method also allows stress to be monitored
continuously
103
.

A brief comparison with Sulfamate Nickel.

Intrinsic stress is the internal stress associated with the deposit, only without influence of the
material onto which it is plated. Stress is induced when metals change temperature. Thus, when
using stress test methods, which require plating onto a helix or onto other forms of metal, the
stress values observed will be different at different temperatures.

It is important to zero the instrument used for stress testing (e.g., spiral contractometer) at the
temperature at which the reading is to be taken; for example, the plating solution temperature.
The result is the intrinsic stress of the deposit. This method provides more consistent test results.
The thickness of the deposit must be accurately controlled and known. The stress readings will
be significantly different for different thicknesses. Correction factors do not fully compensate
for thickness variations.


Stress is reported in pounds per square inch (PSI) or, most often, in megapascals (MPa). Other
terms are sometimes used. Nickel sulfamate solutions, which are made from pure chemicals and
do not have codepositing addition agents, will produce deposits with from 0 to 4,000 psi (about
27.8 megapascals). The very lowest stress Its been achieved using a Watts nickel formulation
(nickel sulfate, 42 oz/gal; nickel chloride, 8 oz/gal; boric acid, 6 oz/gal); carbon treated and
electrolytically purified; and using the purest chemicals available was 26,000 psi (or about 179
megapascals.) More typical of a Watts nickel is about 40,000 psi tensile stress. (There are
literature references that report 20,000 psi tensile stress for Watts nickel solutions). Note, when
primary and secondary brightener addition agents are added in proper amounts, the stress is
reduced, but the deposit is considerably more brittle, and harder. Sulfamate nickel deposits are
not only low stress, but ductile as well.

Stress in plated deposits can be tensile or compressive. Tensile stress occurs when the deposit
tries to contract. If plated on one side of a thin flexible metal strip, the metal would bend in the
direction of the deposit. Compressive stress occurs when the deposit tries to expand. The metal
strip would then bend away from the deposit. High tensile stress can cause spontaneous
cracking of the deposit, and if adhesion is marginal, peel away from the basis metal in a curl
type of exfoliation. Low tensile stress is not harmful unless the deposit is on glass, where there
is little or no adhesion. Low tensile stress can sometimes be beneficial, as in the case of
sulfamate nickel where the maximum ductility (elongation) occurs at from 300 to 5,000 psi
tensile. Compressive stress in a sulfamate nickel deposit could indicate impurities. A low
compressive stress in a deposit from sulfamate nickel solution will improve fatigue life of
hardened steels. High compressive stress can cause the deposit to blister if adhesion is marginal.
Plating onto plastics, where adhesion is marginal compared with plating onto metals, from
1,000 psi tensile to 1,000 psi compressive seems to work best.

Note, the accuracy/reproducibility of the tests can vary by several hundred psi. The spiral
contractometer test run by the same person, following all the procedures very carefully, can
expect a variation of about 100 psi
104
. How high is high stress? This is best answered by
comparing a few plated deposits. Chromium plating in the decorative range is usually from
90,000 to 200,000 psi tensile. Watts nickel without addition agents is about 26,000 to 45,000 psi
tensile. Copper from cyanide solutions, without addition agents, is about 5,200 to 15,000 psi
tensile. Acid copper, without addition agents except for about 50 ppm chloride, is about 100 to
500 psi tensile. Specification AMS 2416 (aerospace material specification) defines low stress
sulfamate nickel as 15,000 tensile stress as maximum for low stressed deposits. These
numbers seem large, but if reported in megapascals, 1,500 psi would be approximately 10.3.
105


Structure and mechanical properties of electrodeposits.

Roehl, Brenner at al., and Heussner et al., reported a wealth of data on the effects of pH,
temperature, current density, and solution composition on the metallographic structure and
mechanical properties of Nickel deposits from the Watts bath. These effects can be summarized
in a general way as follows.

When plated at 55C and pH 2.0, deposits show a columnar or conical structure which grows
coarser with increasing thickness. Grain refinement occurs as the pH or the chloride content is
increased or the temperature is decreased. The effect of current density varies with conditions.
related; that is, an increase in hardness is accompanied by an increase in tensile strength and a
decrease in ductility.

Soft ductile deposits are obtained at pH 4.5 or lower. For example, a tensile strength of 35
kg/mm
2
, an elongation of 37%, and a Vickers diamond hardness (10kg-load) of 100 were
observed by Roehl in nickel electrodeposited at pH 4.5. As pH was decreased below 3 the
hardness rose slowly, bur as pH was increased above 5 it rose rapidly, with a corresponding
increase in tensile strength and reduction in ductility.

Current densities over the range 1 to 5 A/dm
-2
had little effect on the mechanical properties of
the deposit from the low pH bath, but at pH 5.0 there appeared to be some decrease in hardness
and tensile strength with increasing the current density in range. Brenner and Jeannings
obtained a Knoop hardness (200-g load) of 175 in a bath at pH 30.0 and a low current density of
1 A/dm
2
. They found that the hardness reached a minimum of 135 at 4 A/dm
2
and then
increased slowly with further rise in current density. An increase in temperature of the
electrolyte had the expected effect of decreasing hardness and tensile strength and increasing
ductility.

The increase in hardness and tensile strength of nickel deposits produced at high pH has been
shown by Macnaughtan et al., to be related to the amount of occluded basic compounds of
nickel. These are believed to be codeposited in a finely divided or colloidal from dispersed
through the nickel lattice in such a way as to interfere with slip.

Nickel can be deposited with a wide variety of metallographic structures and with controlled
physical and mechanical properties over a wide range of values. When other than a soft, ductile
nickel is required, additives or bath compositions quite different from the Watts solution are
employed.

Stress.

An important, complex, and not very well understood characteristic of nickel deposits is that all
are deposited in a condition of internal contractile (tensile). Class I and II addition agents
greatly affect the stress. The internal stress in nickel plate has received extensive study more
than for any other plated metal.

The stress that arises independently of the substrate is called the intrinsic stress. It is
superimposed on an extrinsic stress induced by the substrate, though the effect of the latter is
only in the first thin layers of the deposit. The stress of primary interest to electroplaters is the
elastic tensile or compressive stress which can be measured by mechanical means, and this is
what is generally meant when the word stress is used in electroplating. This stress is also
referred to as macrostress or type I stress. Its magnitude is important since excessive tensile
stress in nickel deposits can not only lead to gross cracking of the plate but also can cause
distortion of electroforms. These problems accelerated the development of methods to measure
such stresses quantitatively. Measurements were primarily based on the amount of bending of a
strip, nickel plated only on one side.

Besides the elastic macrostress, there are microstresses which have been classified as types II
and III stresses. Microstresses do not cause macroscopic deformation and can be determined
only by methods such as measurement of X-ray line widening. In the theoretical work of Hoar
and Arrowsmith, Krner, Popereka and others, on the origins of internal stress, the theory dos
dislocations in metals have been used as the basis for an overall theory. For example, the
movement of dislocations to the grain boundaries may be the cause of tensile stress according to
Popereka. The regulated incorporation of the sulfide anion, which is larger than the nickel
cation, appears to be an important factor in the origin of compressive stress in nickel. The larger
size of the sulfide anion and its effect on increasing the rate of nucleation would favor
expansion at the grain boundaries. The extensive literature on the origins of stress in
electrodeposits and the methods of measurement has been reviewed by Weil.


Effect of the bath variables.

Regardless of the mechanism, the practical plater wants to know how the major plating
variables influence internal stress in nickel deposits The preponderance of evidence supports the
following conclusions:

1. Tensile stress increases with increase in chloride content of the bath.
2. The effect of bath temperature on stress is not consistent; it varies with the composition
of the bath (principally the chloride content) and the current density.
3. The effect of pH varies with composition of the electrolyte; however, for a Watts bath it
is definitely advisable to keep the pH below 5, not only because deposit with lower
stress are obtained but also because the harmful effects of some impurities on stress
may be much more pronounced at pH 5 or above.
4. The effect of current density is not marked over the range 1 to 5 A/dm
2
but is usually in
the direction of an increasing tensile stress with increasing current density.
5. Superimposing alternating current on the direct plating current tends to reduce stress,
other conditions remaining the same.
6. Agitation has little effect in purified plain Watts baths. In bright plating baths
containing excessive concentrations of class II brighteners or harmful impurities,
decreased agitation (decreased diffusion rate) will result in decreased tensile stress.
7. Hydrogen peroxide, dissolved inorganic impurities such as lead, zinc, iron, chromium,
aluminum, and phosphate, organic impurities such as sizing from unwashed anode bags,
amines from improperly cured rubber linings, and excessive concentrations of class II
brighteners can all act to increase the tensile stress seriously.
8. Fluorides and fluoborates tend to reduce tensile stress slightly. Class I brighteners can
decrease the tensile (contractile) stress to zero and then with increasing concentrations,
reverse the direction so as to make the nickel expand or be under compression if
restrained from expanding. These organic sulfon compounds add sulfur as sulfide to the
nickel deposit, increasing the hardness of the deposit and its tensile strength, but
decreasing its ductility and making the plate very brittle (sulfur embrittlement) when
heated to temperatures above 370C. Adhesion to steel is not lost however.
9. Stress may be induced into the first thin layers of a plate that is deposited on a
structurally different substrate with different lattice spacing or on a substrate that has a
high internal stress in the surface. Highly tensile stressed nickel plate can cause the
usual thin, highly tensile stressed decorative chromium plate to stress crack at the same
time as the nickel stress cracks from the added tensile stress of the chromium plate.

Stress versus ductility.

It is important to differentiate between the deleterious effects of high stress and lack of ductility.
There are no predictable relationships between hardness, brittleness and stress. Relatively soft
deposits from the Watts bath may be highly stressed in tension and show good ductility,
whereas nickel deposited in the presence sodium naphthalene trisulfonate can show zero stress
with a Vickers hardness of 540 and a low ductility.


Phase 4: Hypothesis.

Idea/proposal 1:

Based on what we have seen in the investigation we can link the theory with the production line.
Assuming pH, current density and temperature steady and controlled. The stress of the
electrodeposit produced by Nickel Spectra bath depends on:
I. Carrier concentration.
II. Brightener concentration.
III. Wetting agent concentration.
IV. Chloride concentration.
V. The amount of pollution either organic or inorganic.


Idea/proposal 2:

If, as referred above, adhesion onto the substrate is marginal, a high compressive stress can
cause the deposit to blister. Thats why stress is considered a factor on blistering problems, if
this is compressive and its value its particularly high.


Phase 5: Test plan creation.

To define which tests will be performed:

In order to evaluate what we stated to be the variables that influence the stress produced by the
Nickel Spectra bath in the production line, different solutions will be evaluated at different
concentrations of:
I. Carrier
II. Brightener
III. Wetting Agent
IV. Chloride
V. Pollution either organic or inorganic

At the same time, the values of the stress produced by Nickel Spectra bath will be monitored
periodically to characterize its magnitude and nature.

Test plan building:

Test 1.- Evaluate the reliability of the device used to measure stress.
Test 2.- Sample of the Bath (Spectra)
Test 3.- Sample of the Bath (PC3)
Test 4.- Evaluation of the Effect of Carbon Treatment on the Spectra Bath (Before Treatment,
After Treatment, After Replenishment)
Test 5.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 50, 100, 150)%
Test 6.- Watts Solution 50% Cl
-
+ Variation of Brightener (0, 50, 100, 150)%
Test 7.- Watts Solution 50% Cl
-
+ Variation of Wetting Agent (0, 50, 100, 150)%
Test 8.- Watts Solution 50% Cl
-
+ Variation of Copper Pollution (0, 5, 10, 20, 100, 200)ppm
Test 9.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 10, 20, 30, 40, 50, 60, 70, 80, 90,
100)%
Test 10.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 100)%
Test 11.- Watts Solution 50% Cl
-
+ Carrier (100%) + Wetting Agent (100%)
Test 12.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 50, 100, 150, 200, 250, 300)%
Test 13.- Watts Solution 100%Cl
-
+ Variation of Carrier (0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30,
40, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300)%
Test 14.- Watts Solution 100% Cl
-
+ Variation of Copper Pollution (0, 5, 10, 20, 100, 200)ppm
Test 15.- Watts Solution 100% Cl
-
+ Carrier (100%) + Wetting Agent (100%)

Note al percentages are referred to the optimum established in FIP MEX 5 102
Carrier optimum (100%) = 10mL/L
Brightener optimum (100%) = 0.6mL/L
Wetting Agent Optimum (100%) = 2mL/L
Maximum Copper Pollution Tolerance = 30ppm

Test plan implementation:

The device used to measure stress was a stress analyzer based on the bent strip method. The
equipment includes:
- A plating cell made of PVC of 3.21 L
- An immersion heater
- A submersible pump
- 2 Nickel anodes
- Test strips PN: 2042B (Ni-Iron Alloy) used for tensile stresses only
- Test strips PN: 1194 (Cu-Iron Alloy) used for both tensile and compressive stresses
- A deposit stress analyzer

The operation conditions of all the tests were:

- Current density: 5.38 Adm
-2
*
- Temperature: 54-56C**
- pH: 4.3-4.6** (except for the samples of bath solutions in which case pH wasnt
adjusted, it was registered and the strip was plated at the pH the solution had.
- Time: 144 s

The stress was calculated using a variation of the Stoney equation:

! !
!"#
!!
(1)

where
S: is the internal stress expressed in PSI
U: is the number of increments (read in the scale of the stress analyzer); by convention if
looking the strip perpendicularly to the scale, the ends of the legs are plated, the stress in tensile
and U is a positive number; on the other hand if looking the strip perpendicularly to the scale,
the ends of the legs are not plated, the stress in compressive and U is a negative number.
K: is the strip calibration constant (provided by the supplier)
M: is the modulus of elasticity of the deposit divided by the modulus of elasticity of the
substrate material
T: is the deposit thickness in inches, measured by X-Ray fluorescence

The choice of this formula among the many other available obey to the simplicity of it, which
makes it a very good approximation and its easy to handle for routine analysis. It doesnt
involve complex calculus that may confuse the person in charge of the determination.

For a discussion about the method of measurement of analysis and a further discussion of the
fundamentals of the Stoney formula, please refer to appendix A.

Description of the procedure:

Take a 4L sample of the bath or the prepared solution.
Make sure that the flux intensity on the submersible pump is set on level 1
Set the submersible pump on the bottom of the plating cell with the flux exit aiming to one of
the flow holes, and attach the submersible pump to the wall of the plating cell using the suckers
of the pump.
Place the heater in the cell, make sure that it fits with the protrusion of the cell intended to this.
Place the anodes in the cavities intended for this purpose.
Carefully gauge 4.21L of the solution and pour it into the cell.
Plug in the submersible pump (never run the pump dry!) and set the intensity of the heater in
level 4.
Plunge the potentiometer and the thermometer in the solution and monitor it until it reaches (54-
56C), once it reaches this temperature register the pH value.
Immerse the test trip in alkaline cleaner solution at 60C for 30 seconds.
Rinse the test strip in deionized water for 15 seconds.
Immerse the test strip in a H
2
SO
4
or HCl (10% v/v) solution for 30 seconds to activate it.
Rinse the test strip in deionized water for 15 seconds.
Immerse the test strip and in it up with the cathodic clamp of the supply power (rectifier) in the
metallic protrusion that is in the middle of the cell (Fig. 45).
With the anodic clamp of the power supply (rectifier) fix it in the metallic square which
distributes the current to the anodes. And clamp the anodes with the anodes as well (Fig. 45).
Make sure both terminals do not touch each other!


Figure 45. Detail of the plating cell operation for determining stress

Turn on the power supply and fix the current density (I) in 0.416 Ampere (A)
Plate the strip for 144 seconds making sure that the terminals do not touch each other and that
the strip does not touch the anodes (any of those conditions will make the display of the power
supply to show a zero value on (I) and (V).
After the 144 seconds, turn off the supply power.
Remove the test strip and rinse it 15 seconds in deionized water.
Flash rinse the test strip in isopropanol (isopropyl alcohol).
Hang the test strip and wait until it dries.
Once the strip is dry, identify it and place in in the stress analyzer. Watching perpendicularly to
the scale measure the distance between the ends of the legs of the strip. Remember to assign the
sing of this value as discussed before. Register this value as U.
Take the strip to the X-Ray fluorescence apparatus and measure (using the correct calibration)
three spots over the plated side of one leg of the strip. Evaluate the arithmetic mean of these
values, and register this value as T.
Convert T to inches, remember T must be in inches to use it in the formula. If the values are in
micrometers use this conversion factor:

Thickness in (micrometers) x 0.00003937 = Thickness in inches

Calculate the internal stress of the deposit using the equation (1).

Once calculated the stress, the result given in PSI convert ir to MPa by using the following
conversion factor:

Stress (in PSI) x 0.006894 = Stress (in Mpa)



According to this, the tests planned for this study were done, here are the descriptions and
results:


Test 1. Evaluate the reliability of the device used to measure stress

This test was done on December the 27
th
2013 with the solution of the electrolytic nickel bath
Spectra in Radiall Obregn.

A sample of the bath was taken and according to the procedure stated before, the stress of the
deposit it produced was measured using the strips.

Chemical analysis was done to determine the chemical parameters of the solution at that
moment.

The results are as follows:

Nickel Spectra Bath Dec 27
th
27/12/2014 Optimum
Ni
2+
(g/L) 68.21 70
Cl
-
(g/L) 10.7837 18
H3BO3 (g/L) 44.903 45
Current density (A/dm
2
) 5.38 5.38
Time (s) 144 144
pH 4.4 4.3-4.6
Temperature (C) (54-56) 55
Plating cell volume (L) 3.21
Substrate Ni-Iron Alloy
42

Table 13. Spectra bath solution composition analysis. Date december 27
th
2013

Five test strips were plated and the stress of the deposit was measured, the results were:


# Strip Stress (MPa) Variance Standard
Deviation
1 -146.048 110.200 11.737
2 -134.457

3 -153.002

4 -134.457

5 -161.348


Table 14. Stress results of test done to the Spectra solution. Variance and standard deviation
were calculated using Microsoft Excel datasheet.




Figure 46. Stress difference among the strips plated.

Test 2. Spectra stress historical record.


In order to determine and characterize the magnitude and nature of the stress produced by
Spectra electrolytic nickel bath, samples were taken periodically and were tested to measure the
stress of the deposit produced. The chemical analysis and operation conditions can be consulted
in appendix B. All of stress values were recorded and the results were:

Week Stress (MPa) Variance Standard
Deviation
1 -160.067 45.115 7.080
2 -153.002

3 -157.246

4 -166.912

5 -153.002

6 -158.703

7 -153.002

8 -151.264

9 -172.873

10 -153.002

Table 15. Stress values of Nickel Spectra bath evaluated since Week 1 until Week 10

-180
-160
-140
-120
-100
-80
-60
-40
-20
0
1 2 3 4 5
S
t
r
e
s
s

(
M
P
a
)

Number of strip
Stress difference among strips

Figure 47. Weekly stress behavior of the Spectra bath


Test 3. PC-3 stress historical record.

As described before the sulfamate based nickel bath produces deposit with lower values of
stress. The sulfamate nickel PC-3 that is in operation in Radiall Obregn was monitored since
week 4 to know the magnitude and nature of the stress of the deposit that produces.

The chemical analysis and operation conditions can be found in appendix C.

The results were:

Week Stress (MPa) Variance Standard
Deviation
3 -67.680 17.115 4.532
4 -67.680

6 -65.629

8 -56.400

9 -68.755

10 -65.629

Table 16. Stress values of Nickel PC-3 from week 3 to week 10.

-175
-170
-165
-160
-155
-150
-145
1 2 3 4 5 6 7 8 9 10
S
t
r
e
s
s

(
M
P
a
)

Week
Weekly stress behavior of the Spectra bath

Figure 48. Weekly stress behavior of the PC-3 bath.

Test 4.- Evaluation of the Effect of Carbon Treatment on the Spectra Bath (Before
Treatment, After Treatment, After Replenishment)

The spectra solution undergoes carbon treatment twice a week. As result of this its been
observed a decrease in blisters on the pieces. The effect on the stress of the carbon treatment
was evaluated every time it was done to the solution.

The chemical composition of the solutions and the operation conditions can be found in
appendix D.

The values of stress when carbon treatment was done to the solutions are:

Week Date Beofre
Treatment
After
Trestment
After
Replenishment
2 08-ene -156.143 -143.131
12-ene -162.649 -140.568
3 15-ene -136.434 -138.658
19-ene

4 22-ene -168.071 -156.143 -169.155
26-ene -138.658 -128.345 -151.264
5 29-ene -163.869 -156.143 -165.015
02-feb

6 05-feb -167.403 -144.385 -175.325
09-feb -172.855 -142.351 -160.428
7 12-feb -183.023 -144.385 -185.638
16-feb -177.866 -154.698 -183.023
8 19-feb -155.671 -156.940 -180.481
23-feb

9 26-feb -160.428 -136.580 -183.175
02-mar -156.940 -142.351 -185.638
10 05-mar -160.428 -146.477 -172.855
Table 17. Carbon treatment effect in the stress.

-70
-68
-66
-64
-62
-60
-58
-56
-54
-52
-50
3 4 5 6 7 8 9 10
S
t
r
e
s
s

(
M
P
a
)

Week
Weekly stress behavior of the PC3 bath

Figure 49. Carbon treatment effect in the stress as recorded by date.

Test 5.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 50, 100, 150)%

To evaluate the effect of the carrier on the internal stress of the deposit produced by electrolytic
nickel solutions a new Watts solution was prepared simulating the Spectra bath, This Watts
solution was prepared without additives and small amounts of carrier (5mL/L, 10mL/L, and
150mL/L, that is 50%, 100%, and 150% of the optimum values of carrier) were added. The
stress produced by the solution with the different amounts of carrier were registered.

The results are as follows:

Component concentration Watts (09-01)
Ni
2+
(g/L) 69.21
Ci
-
(g/L) 10.783
H3BO3 (g/L) 44.903
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.46
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Ni-Iron Alloy 42
Table 18. Solution composition of the Watts solution and operational parameters for carrier
effect on the stress test.


Carrier % Stress (MPa)
0 146.680
50 -102.632
100 -146.680
150 -148.298
Table 19. Stress values for different concentrations of carrier.
!"##
!%&#
!%'#
!%(#
!%)#
!%*#
!%+#
!%,#
!%"#
#%!-.- %%!-.- "%!-.- ,%!-.- %#!/-0 "#!/-0 #"!123 %"!123
4
5
3
-
6
6

7
8
9
2
:

;25-
<230=. 53-251-.5 -//->5 ?. 5@- 653-66 0-@2A?=3
B-/=3- 53-251-.5 C/5-3 53-251-.5 C/5-3 3-DE-.?6@1-.5


Figure 50. Stress values at different concentrations of carrier.

Test 6.- Watts Solution 50% Cl
-
+ Variation of Brightener (0, 50, 100, 150)%

To evaluate the effect of the brightener on the internal stress of the deposit produced by
electrolytic nickel solutions a new Watts solution was prepared simulating the Spectra bath,
This Watts solution was prepared without additives and small amounts of brightener (0.3mL/L,
0.6mL/L, and 0.9mL/L, that is 50%, 100%, and 150% of the optimum values of brightener)
were added. The stress produced by the solution with the different amounts of brightener were
registered. The solution composition and operational parameters are:

Component concentration Watts (09-01)
Ni
2+
(g/L) 70.34
Ci
-
(g/L) 9.93
H3BO3 (g/L) 45.12
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.53
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Ni-Iron Alloy 42
Table 20. Solution composition of the Watts solution and operational parameters for brightener
effect on the stress test.


Brightener (%) Stress (MPa)
0 152.332
50 403.370
100 #VALOR!
150 #VALOR!
Table 21. Stress values for different concentrations of brightener

!%(#
!%"#
!(#
!"#
,#
'#
%,#
# "# +# )# '# %## %"# %+# %)#
4
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ <233?-3
H//->5 =/ 5@- >233?-3 =. 5@- 653-66 =/ 5@- I-D=6?5J

Figure 51. Stress values at different concentrations of brightener.

The stress values for the 100% and 150% concentration of brightener are missing because the
produced a very high stress deposit, and their values couldnt be measured with the analyzer
used for this purpose.


Test 7.- Watts Solution 50% Cl
-
+ Variation of Wetting Agent (0, 50, 100, 150)%

To evaluate the effect of the wetting agent on the internal stress of the deposit produced by
electrolytic nickel solutions a new Watts solution was prepared simulating the Spectra bath,
This Watts solution was prepared without additives and small amounts of wetting agent (1mL/L,
2mL/L, and 3mL/L, that is 50%, 100%, and 150% of the optimum values of brightener) were
added. The stress produced by the solution with the different amounts of wetting agent were
registered. The solution composition and operational parameters are:

Component concentration Watts (16-01)
Ni
2+
(g/L) 69.87
Ci
-
(g/L) 10.02
H3BO3 (g/L) 45.03
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.46
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Ni-Iron Alloy 42



Table 22. Solution composition of the Watts solution and operational parameters for wetting
agent effect on the stress test.







#
*#
%##
%*#
"##
"*#
,##
,*#
+##
+*#
# %# "# ,# +# *# )#
4
5
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ 03?K@5-.-3
H//->5 =/ 03?K@5-.-3 =. 5@- 653-66 =/ 5@- I-D=6?5
Wetting agent
(%)
Stress (MPa)
0 146.680
50 140.568
100 134.457
150 146.680
Table 23. Stress values for different concentrations of wetting agent.


Figure 52. Stress values at different concentrations of wetting agent.


Test 8.- Watts Solution 50% Cl
-
+ Variation of Cu pollution (0, 5, 10, 20, 100, 200
ppm)

To evaluate the effect of the Cu pollution on the internal stress of the deposit produced by
electrolytic nickel solutions a new Watts solution was prepared simulating the Spectra bath,
This Watts solution was prepared without additives and small amounts of Copper as CuSO
4
-
(5, 10, 20, 100 and 200 ppm) were added. The stress produced by the solution with the different
amounts of Cu were registered. The solution composition and operational parameters are:


Component concentration Watts (16-01)
Ni
2+
(g/L) 70.35
Ci
-
(g/L) 9.56
H3BO3 (g/L) 44.75
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.42
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Ni-Iron Alloy 42



Table 24. Solution composition of the Watts solution and operational parameters for Cu
pollution effect on the stress test.


%,"
%,+
%,)
%,'
%+#
%+"
%++
%+)
%+'
# "# +# )# '# %## %"# %+# %)#
4
5
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ L-55?.K 2K-.5
H//->5 =/ L-55?.K 2K-.5 =. 5@- 653-66 =/ 5@-
I-D=6?5

Cu (ppm) Stress (MPa)
0 146.680
5 162.649
10 148.936
20 115.248
100 111.702
200 100.842
Table 25. Stress values for different concentrations of Cu pollution.


Figure 53. Stress values at different concentrations of wetting agent.

Test 9.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 10, 20, 30, 40, 50, 60, 70, 80,
90, 100)%

As seen before, carrier has a very strong effect on the stress of the deposit. To comprehend
better its influence it was decided to evaluate this influence by making smaller additions to a
new Watts solution and evaluate the effect of the carrier on the stress of the deposit.

This time smaller additions of carrier were done to the solution (1mL/L, 2mL/L, 3mL/L, 4mL/L,
5mL/L, 6mL/L, 7mL/L, 8mL/L, 9mL/L, 10mL/L and 1.5mL/L that is 10, 20, 30, 40, 50, 60, 70,
80, 90, 100, and 150%). The results are as follows:

Component concentration Watts (12-02)
Ni
2+
(g/L) 69.42.
Ci
-
(g/L) 10.32
H3BO3 (g/L) 45.5
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.4
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy



&#
%##
%%#
%"#
%,#
%+#
%*#
%)#
%(#
# *# %## %*# "##
4
5
3
-
6
6

7
8
9
2
:

<G 7DD1:
H//->5 =/ <G D=EEG5?=. =. 5@- 653-66 =/ 5@-
I-D=6?5
Table 26. Solution composition of the Watts solution and operational parameters for carrier
effect on the stress test additions each 10%-.

Carrier (%) Stress (MPa)
0 180.481
10 -135.361
20 -174.659
30 -180.481
40 -186.303
50 -186.303
60 -186.303
70 -204.545
80 -197.947
90 -216.577
100 -209.591
150 -240.642

Table 27. Stress values for different concentrations of carrier each 10% of the optimum.


Figure 55. Stress values at different concentrations of carrier with smaller additions of it each
10%-


Test 10.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
100)%

As seen before even with smaller additions of carrier the change on the stress was very fast.
Because of this a new test was performed to characterize the behavior of the stress at very small
amounts of carrier (<10%). A new Watts solution was prepared simulating the Spectra bath,
This Watts solution was prepared without additives and small amounts of carrier (0.1mL/L,
0.2mL/L, 0.3mL/L, 0.4mL/L, 0.5mL/L, 0.6mL/L, 0.7mL/L, 0.8mL/L, 0.9mL/L, 1mL/L were
added. The stress produced by the solution with the different amounts of carrier were registered.

The solution composition and operational parameters are:


!"*#
!"##
!%*#
!%##
!*#
#
*#
%##
%*#
"##
!%# %# ,# *# (# &# %%# %,# %*#
4
5
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ >233?-3
H//->5 =/ >233?-3 >=.>-.5325?=. =. 5@- 653-66 =/
5@- I-D=6?5



Component concentration Watts (21-02)
Ni
2+
(g/L) 69.65
Ci
-
(g/L) 10.19
H3BO3 (g/L) 44.3
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.49
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy



Table 28. Solution composition of the Watts solution and operational parameters for carrier
effect on the stress test each 1%-

Carrier (%) Stress (MPa)
0 175.012
1 -11.107
2 -86.200
3 -127.398
4 -144.385
5 -155.491
6 -153.136
7 -153.136
8 -153.136
9 -153.136
10 -153.136
Table 29. Stress values for different concentrations of carrier each 1% of the optimum.



Figure 56. Stress values at different concentrations of carrier with smaller additions of it each
1%-

!"##
!%*#
!%##
!*#
#
*#
%##
%*#
"##
# % " , + * ) ( ' & %#
4
5
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ >233?-3
H//->5 =/ >233?-3 >=.>-.5325?=. =. 5@- 653-66 =/
5@- I-D=6?5

Test 11.- Watts Solution 50% Cl
-
+ Carrier (100%) + Wetting Agent (100%)

To simulate the conditions of the real bath, a small one was prepared in the laboratory with the
same concentrations of electrolytes and additives. The stress was measured to compare this
value with the one in the production line.

The solution composition and operational parameters are.

Component concentration Watts (20-02)
Ni
2+
(g/L) 70.62
Ci
-
(g/L) 10.15
H3BO3 (g/L) 45.25
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.43
Temperature (C) 55.5
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy



Table 30. Solution composition of the Watts solution and operational parameters recreation of
the simulation bath.

Test Stress (MPa) Variance Standard
Deviation
1 -165.325 9.482984 3.771534966
2 -160.423

3 -167.839


Table 31. Stress values of the deposit produced by a bath prepared simulating the conditions in
the production line.

Test 12.- Watts Solution 50% Cl
-
+ Variation of Carrier (0, 50, 100, 150, 200, 250,
300)%

Weve noticed that at a certain point the amount of carrier added to the solution has no further
effect on the stress of the deposit produced by the solution. A new Watts solution was prepared
and carrier was added in excess to evaluate the influence on the stress of this excess.

Solution composition and operation parameters are:

Component concentration Watts (25-02)
Ni
2+
(g/L) 69.25
Ci
-
(g/L) 10.43
H3BO3 (g/L) 45.65
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.45
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy


Table 32. Solution composition of the Watts solution and operational parameters for carrier
excess influence on the stress.
Carrier (%) Stress (MPa)
0 203.041
50 -180.481
100 -203.041
150 -225.601
200 -214.321
250 -225.601
300 -225.601
Table 33. Stress values of the deposit produced by a bath with excess of carrier.


Figure 57. Stress values at different concentrations of carrier until its added an excess of it.

Test 13.- Watts Solution 100%Cl
-
+ Variation of Carrier (0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
20, 30, 40, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300)%


Since a mistake was discovered in the FIP MEX 5 102 which is the one that states the
composition and parameter operations of the Spectra bath, (the discussion for this error and its
correction can be found in appendix E) a solution with the optimum concentration of chloride
was prepared and the stress was evaluated in this conditions. As seen before, of the variables we
have in the line, carrier concentration has been demonstrated to be very important, so variations
of carrier were done to the solution to evaluate the behavior of the stress.

The solution composition and operational parameters are:

Component concentration Watts (27-02)
Ni
2+
(g/L) 70.05
Ci
-
(g/L) 18.13
H3BO3 (g/L) 45.05
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.4
Temperature (C) 54-56
!"*#
!"##
!%*#
!%##
!*#
#
*#
%##
%*#
"##
"*#
# *# %## %*# "## "*# ,##
4
5
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ >233?-3
HM>-66 =/ >233?-3 2.I ?56 ?.NEG-.>- =. 5@- 653-66
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy


Table 34. Solution composition of the Watts solution and operational parameters with the
optimum concentration of chloride and variations of carrier each 1% from 1% to 10%, each
10% from 10% to 100% and each 50% from 100% to 300%-

Carrier (%) Stress (MPa)
0 451.203
1 338.402
2 225.601
3 45.120
4 45.120
5 11.280
6 0.000
7 0.000
8 -67.680
9 -67.680
10 -90.241
20 -124.081
30 -135.361
40 -135.361
50 -135.361
60 -135.361
70 -135.361
80 -135.361
90 -135.361
100 -135.361
150 -135.361
200 -135.361
250 -135.361
300 -135.361

Table 35. Stress values of the deposit produced by a Watts solution with the optimum
concentration of chloride and a variation of carrier concentration.




Figure 58. Stress values at different concentrations of carrier and the optimum value of chloride
concentration

Test 14.- Watts Solution 100% Cl
-
+ Variation of Copper Pollution (0, 5, 10, 20, 100,
200)ppm

In order to evaluate the influence of Cu pollution this time on a bath that has the optimum
concentration of chloride a new Watts solution was prepared and small amounts of Cu (as
CuSO
4
) were added -5, 10, 20, 100 and 200 ppm-.

!%*#
!*#
*#
%*#
"*#
,*#
+*#
# *# %## %*# "## "*# ,##
4
5
3
-
6
6

7
8
9
2
:

F =/ 5@- =D5?1G1 =/ >233?-3
453-66 0-@2A?=3 =/ 2 O2556 6=E?5?=. L?5@ 5@-
=D5?1G1 =/ >@E=3?I- 2.I A23?25?=. =/ >233?-3
The operation conditions and solution composition are:

Component concentration Watts (27-02)
Ni
2+
(g/L) 70.21
Ci
-
(g/L) 18.02
H3BO3 (g/L) 45.4
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.44
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy


Table 36. Solution composition of the Watts solution and operational parameters with the
optimum concentration of chloride and variations of Cu pollution -5, 10, 20, 100 and 200 ppm-

Cu (ppm) Stress (MPa)
0 442.534
10 437.432
20 440.783
100 431.652
200 437.838

Table 37. Stress values obtained with the optimum concentration of chloride and variations of
Cu pollution -5, 10, 20, 100 and 200 ppm-


Figure 59. Stress values at different concentrations of Cu pollution and the optimum value of
chloride concentration


Test 15.- Watts Solution 100% Cl
-
+ Carrier (100%) + Wetting Agent (100%)

To simulate what the stress value of the spectra bath would be if the chloride concentration was
at the optimum, a new solution was prepared exactly the way the Spectra bath is prepared with
the correction of chloride value.

+,#
+,"
+,+
+,)
+,'
++#
++"
+++
# "# +# )# '# %## %"# %+# %)# %'# "##
4
5
3
-
6
6

7
8
9
2
:

<G 7DD1:
453-66 0-@2A?=3 =/ 2 O2556 6=EG5?=. L?5@ 5@-
=D5?1G1 A2EG- =/ >@E=3?I- 2.I <G D=EEG5?=. 25
I?//-3-.5 DD1
The operation parameters and solution composition are:

Component concentration Watts (27-02)
Ni
2+
(g/L) 70.21
Ci
-
(g/L) 18.02
H3BO3 (g/L) 45.4
Current density (A/dm
2
) 5.38
Time (s) 144
pH 4.44
Temperature (C) 54-56
Plating cell volume (L) 3.21
Susbtrate Cu-Iron Alloy


Table 38. Solution composition of the Watts solution that simulates the Spectra bath with the
optimum value of chloride

Test Stress Variance Standard
Deviation
1 -120.325 1.430952 1.465069282
2 -117.415

3 -118.573

Table 39. Stress values for a Watts solution with the optimum concentration of chloride
simulating the Spectra bath.

Compare results between themselves and find a trend or a correlation factor.

Analyzing all the information we can see that:

1.- Stress can be either tensile or compressive.
2.- We define positive values for tensile stress and negative values for compressive stress.
3.- A Watts solution without additives has a tensile stress.
4.- As carrier concentration goes up, the tensile stress value goes down, when enough carrier
has been added the resultant stress is compressive.
5.- As brightener concentration goes up, the tensile stress value goes up. That means if the stress
is tensile, brightener will make it even more tensile, the deposit then becomes brittle and it peels.
6.- Neither wetting agent concentration nor Cu pollution concentration showed a relation with
the behavior of stress.
7.- As chloride concentration goes up, the tensile stress goes up.
8.- When enough carrier is added to the solution it saturates the solution and has no effect
beyond this point.
9.- The Spectra bath has showed always a compressive stress.
10.- The PC-3 bath has showed always a compressive stress but its value is lower than the
Spectras value.
11.- When making the simulation of the bath, the one with the optimum concentration of
chloride presented a lower compressive stress value than the one with half chloride
concentration.

Phase 6. Comparison of the test plan results vs hypothesis and the problem.

Remembering hypothesis one we can now tell that:

Assuming pH, current density and temperature steady and controlled. The stress of the
electrodeposit produced by Nickel Spectra bath depends on:

I. Carrier concentration. (True)
II. Brightener concentration. (True)
III. Wetting agent concentration. (False)
IV. Chloride concentration. (True)
V. The amount of pollution either organic or inorganic. (Partially false)


If, as referred above, adhesion onto the substrate is marginal, a high compressive stress can
cause the deposit to blister. Thats why stress is considered a factor on blistering problems, if
this is compressive and its value its particularly high.

We can not tell anything about this yet, because another study to characterize the adhesion is in
order. We can now say blistering has two main contributors: adhesion and stress.

Adhesion = f (adhesion, stress)

It needs both to have the blistering problem. If we fix one of them the blister will disappear, but
the other problem may remain in silence.

This way, if we reduce the stress we know that we stand good chances of improving the
blistering issue, but the lack of adhesion will still be there, it wont manifest as blister because
the stress is revealing it now.

The other way if we fix the adhesion, we wont have blisters either, but well be able to control
the stress because we have a method to determine it now.

Lets remember that the Spectra system is a bright nickel system that is designed to produce
bright deposits. The application that Radiall gives is not bright, because the Spectra bath is run
without brightener.

So if we look carefully inside the system we will notice something. The Spectra bath takes into
account in their technical data sheet that the amount of chloride is between (16-20)g/L, the
amount of brightener is from (0.4-0.8)mL/L, and with those components at those concentrations
the system gives a deposit with a balanced stress value.

The Spectra bath in Radiall is run without brightener and with half the chloride optimum.

We know carrier reduces the tensile stress and increases the compressive stress, we know also
that the brightener reduces compressive stress and increases tensile stress, and finally we know
that chloride reduces compressive stress and increases tensile stress.

The Spectra bath shows a compressive stress, and that may be caused because the optimum
value of carrier is being added to the bath, even though carbon treatment is done to the solution,
carrier is replenished every time the treatment is done. But this bath is lacking the presence of
brightener which should be brightening the pieces, but also increasing the tensile stress. And
because the miscalculation in the chloride analysis, its concentration its half the optimum, so
another contributor of tensile stress is missing.

In other words, the bath is formulated to have certain amounts of components to balance the
stress, right now were at the optimum of carrier (which gives the compressive stress), but were
not adding brightener (which contributes to the tensile stress) and were missing the 50% of
chloride (which contributes to tensile stress also). So if we look at the big picture compressive
stress is winning because the bath is out of balance.


Define if root cause has been found and fixed.

Blistering root cause is as we discussed before a combination of poor adhesion and stress.
Adhesion and stress need to be studied, monitored, and controlled, in order to solve the problem
totally.

Stress can be lowered down, this could partially solve the problem because the blister would not
form, but if the lack of adhesion is there we would not notice it, because the low value of stress
wouldnt neither be compressive enough to form the blister nor tensile enough to make the
deposit peel away. But when an adhesion test is done to this part, it would not pass the test.

Lets remember this study was done in the last layer of the deposit the pieces have. Its
representative because electrolytic nickel has the highest value of stress of all the layers (copper,
electroless nickel) but in order to know more accurately the behavior of the stress in the
production line, each layer should be studied, characterized and monitored. This project is now
on going in Radiall Obregon.

Phase 7: Conclusions.

Stress depends on many factors: current density, pH, chloride content, carrier concentration and
brightener concentration.

Assuming that in the production line the current density, pH, are steady and controlled, stress
depends only on the chloride, carrier and brightener concentration.

The bath is currently out of balance because the carrier is in its optimum value but the chloride
content is in the 50% of the optimum, and no brightener its being added to the bath.

Lowering the stress may partially resolve the blistering issue, because blistering depends on the
stress but also on the adhesion.

Adhesion needs to be studied, characterized, controlled, and monitored in order to solve the
problem completely.

Phase 8: Improvement implementation.

In order to lower the stress produced by the bath, two ways can be taken:

1.- Increase the content of brightener, this will increase the tensile stress giving as result a lower
net stress. The brightener additions must be controlled, because it requires very small amounts
of it. The deposit will become bright, and it will have a mirror-like finish.

2.- Increase the chloride content, this will increase the tensile stress giving as result a lower net
stress. Increasing the chloride will set the bath in the right concentration according to FIP MEX
5 102. Increasing the chloride will give as result:
A higher anode corrosion, so less amount of salts will be needed.
A higher conductivity of the solution, so less voltage will be needed to perform
electrodeposition.

On march the 6
th
a meeting was made. And the Engineering team, with the Quality and
Production teams agreed to wait until the study regarding the roughness (which will improve the
adhesion) is finished. This with the aim of being able to distinguish if an improvement is seen
on the problem is due to the stress or the adhesion.

As soon as a roughness value is defined as optimum for the process, the chloride concentration
on the Spectra bath will be increased gradually.

The plan is to increase the chloride content from 10% to 10% until we reach the optimum value.

The calculations of the amount of salts, additives and solution needed can be consulted in the
excel sheet Nickel solution adjustments

Phase 9: Following up.

Pending.












































Appendix A. The Stoney Formula.
























Appendix B. Solution composition and operational parameters of the historic
record of the Spectra bath.


Component concentration Week 1 Week 2 Week 3
Ni
2+
(g/L) 71.435 70.53 69.12
Ci
-
(g/L) 9.964 9.311 9.725
H3BO3 (g/L) 44.356 45.76 45.611
Current density (A/dm
2
) 5.38 5.38 5.38
Time (s) 144 144 144
Temperature (C) 55.6 55.4 55.3
Plating cell volume (L) 3.21 3.21 3.21
Susbtrate Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42

Week 4 Week 5 Week 6 Week 7
71.213 70.462 71.747 70.346
10.12 10.145 9.364 10.176
44.912 45.725 44.856 46.25
5.38 5.38 5.38 5.38
144 144 144 144
55.7 56.1 55.3 55.5
3.21 3.21 3.21 3.21
Ni-Iron Alloy
42
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Week 8 Week 9 Week 10
70.276 70.014 70.22
10.632 10.513 10.617
45.821 45.1 45.012
5.38 5.38 5.38
144 144 144
55.7 55.2 55.8
3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Appendix C. Solution composition and operational parameters of the historic
record of the PC-3 bath.

Component concentration Week 3 Week 4 Week 6
Ni
2+
(g/L) 70.21 70.51 72.1
Ci
-
(g/L) 7.72 7.45 7.21
H3BO3 (g/L) 40.412 40.23 40.72
Current density (A/dm
2
) 5.38 5.38 5.38
Time (s) 144 144 144
Temperature (C) 55.6 55.4 55.3
Plating cell volume (L) 3.21 3.21 3.21
Susbtrate Ni-Iron Alloy 42 Ni-Iron Alloy 42 Cu-Iron Alloy

Week 8 Week 9 Week 10
72.54 69.64 70.9
7.8 7.51 7.14
40.253 41.22 40.82
5.38 5.38 5.38
144 144 144
55.7 56.1 55.3
3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Appendix D. Solution composition and operational parameters of the historic
carbon treatment performances.

Note:

AT means before treatment
DT means after treatment
DR Means after replenishment

Component
concentration
Spectra AT
08.01
Spectra DT
08.01
Spectra DR 08.01 Spectra AT
12.01
Spectra DT
12.01
Spectra DR
12.01
Ni
2+
(g/L) 70.452 69.8649 71.0391 69.8649 68.6907 70.452
Ci
-
(g/L) 10.1004 9.9232 10.2776 9.9232 9.746 10.2776
H3BO3 (g/L) 45.25 44.9 45.32 44.5 44.3 45.4
Current density
(A/dm
2
)
5.38 5.38 5.38 5.38 5.38 5.38
Time (s) 144 144 144 144 144 144
pH 4.45 4.43 4.39 4.47 4.46 4.38
Temperature (C) 55.6 55.4 55.3 55.7 56.1 55.3
Plating cell volume (L) 3.21 3.21 3.21 3.21 3.21 3.21
Susbtrate Ni-Iron Alloy
42
Ni-Iron Alloy
42
Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42

Spectra AT 15.01 Spectra DT
15.01
Spectra DR 15.01 Spectra AT
19.01
Spectra DT
19.01
Spectra DR 19.01
70.0391 70.452 71.6262 68.6907 67.5165 72.2133
10.1004 9.9232 10.2776 9.746 10.1004 9.9232
45.36 44.78 45.11 44.3 45.6 45.5
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.43 4.45 4.45 4.37 4.36 4.4
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42

Spectra AT 22.01 Spectra DT
22.01
Spectra DR 22.01 Spectra AT
26.01
Spectra DT
26.01
Spectra DR 26.01
70.452 69.8649 70.452 72.2133 70.452 71.0391
9.746 9.5688 9.9232 9.9232 10.1001 10.1001
44.76 45.7 45.1 44.6 45.09 45.9
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.35 4.36 4.39 4.43 4.42 4.43
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42

Spectra AT 29.01 Spectra DT
29.01
Spectra DR 29.01 Spectra AT
02.02
Spectra DT
02.02
Spectra DR 02.02
71.0391 70.452 70.452 69.2778 69.8649 70.452
9.9232 9.5688 9.9232 10.1004 9.746 10.2776
45.65 44.13 45.6 45.5 45.14 45.7
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.47 4.45 4.41 4.39 4.37 4.39
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Ni-Iron Alloy 42 Ni-Iron Alloy 42 Ni-Iron Alloy 42 Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Spectra AT 05.02 Spectra DT
05.02
Spectra DR 05.02 Spectra AT
09.02
Spectra DT
09.02
Spectra DR 09.02
70.452 68.6907 69.8649 69.8649 69.8649 70.452
10.1004 9.5688 9.9232 10.2776 9.9232 10.4548
45.32 44.6 44.9 45.4 45.8 46.2
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.43 4.42 4.44 4.33 4.35 4.39
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Spectra AT 12.02 Spectra DT
12.02
Spectra DR 12.02 Spectra AT
16.02
Spectra DT
16.02
Spectra DR 16.02
69.8649 68.1036 70.452 71.6262 69.8649 71.0391
9.9232 9.5688 10.2776 9.9232 9.9232 10.1004
44.9 44.56 44.6 45.21 45.3 46.2
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.43 4.44 4.43 4.41 4.42 4.41
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Spectra AT 19.02 Spectra DT
19.02
Spectra DR 19.02 Spectra AT
23.02
Spectra DT
23.02
Spectra DR 23.02
69.2778 68.1036 69.8649 70.452 69.8649 71.0391
10.1004 9.746 9.9232 9.746 9.5688 10.1004
45.65 44.3 45.2 45.6 44.8 45.9
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.45 4.44 4.4 4.34 4.37 4.41
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Spectra AT 26.02 Spectra DT
26.02
Spectra DR 26.02 Spectra AT
02.03
Spectra DT
02.03
Spectra DR 02.03
68.6907 68.1036 70.452 70.452 69.8649 71.6262
9.9232 9.746 9.9232 9.9232 9.5688 10.2776
45.34 46.4 45.1 44.7 45.3 45.6
5.38 5.38 5.38 5.38 5.38 5.38
144 144 144 144 144 144
4.42 4.42 4.43 4.41 4.44 4.42
55.6 55.4 55.3 55.7 56.1 55.3
3.21 3.21 3.21 3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Spectra AT 05.03 Spectra DT
05.03
Spectra DR 05.03
69.2778 68.1036 69.8649
9.9232 9.746 10.2776
44.3 45 45.4
5.38 5.38 5.38
144 144 144
4.43 4.44 4.42
55.6 55.4 55.3
3.21 3.21 3.21
Cu-Iron Alloy Cu-Iron Alloy Cu-Iron Alloy

Appendix E. The chloride error and its correction.

The reaction in which the method is based is the following:

Ag
+
+ Cl
!
"AgCl#

Lets calculate the relation factor that relates the volume of AgNO
3
used in the titration
and the Cl
-
concentration in g/L

Lets remember that the stoichiometry for the AgNO
3
and Cl
-
is 1:1, so 1 mole in this
reaction is equal to an equivalent, then Normality is Molarity for the chemical species
involved.

A 2mL sample is taken, expressed in liters is 0.002L

An x (mL) volume is used of AgNO
3
0.1M

Hence:

mol 0001 . 0
L 1
mol 1 . 0
1000mL
L 1
mL x x =
!
"
#
$
%
&
!
"
#
$
%
&
this is the amount of substance present in 2mL
2mL, thus
(0.0001 x mol)
0.002L
35.45g de Cl
!
1 mol de Cl
!
"
#
$
%
&
'
=1.7725x
g
L
of Cl
-


We can notice that 1,7725 times the volume x of AgNO
3
used in the titration gives as
result the Cl
-
concentration in g/L


If we take a 1mL sample, the calculation would be:

xmL
1L
1000mL
!
"
#
$
%
&
0.1mol
1L
!
"
#
$
%
&
= 0.0001xmol this is the amount of substance present in 1mL,
thus
(0.0001 x mol)
0.001L
35.45g de Cl
!
1 mol de Cl
!
"
#
$
%
&
'
= 3.545x
g
L
de Cl
-


If we take a 5mL sample, the calculation would be:

xmL
1L
1000mL
!
"
#
$
%
&
0.1mol
1L
!
"
#
$
%
&
= 0.0001xmol this is the amount of substance present in 5mL,
thus
(0.0001 x mol)
0.005L
35.45g de Cl
!
1 mol de Cl
!
"
#
$
%
&
'
= 0.709x
g
L
de Cl
-


The FIP MEX 5 102 establishes two ways analyze the chloride: one manually, the other using
the automatic titrator. Either way the factor is the same: 3.5, but the sample taken is 2mL.

So either the sample is wrong, because for the factor 3.5 a 1mL sample needs to be taken. Or the
factor is wrong, because for a 1mL sample a 1.7725 need to be used.

The consequences of using 2mL with a factor of 3.5 is that laboratory reports twice the real
value the bath has; so the bath concentration is half what it should be.

Another miscalculation was detected in the procedure that establishes the make up of the bath.
This can be found in the word document: Anlisis de Cloruro (in Spanish), to be translated soon.



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