Technical Article Troubleshooting Decorative Electroplating

Installations, Part 5: Plating Problems Caused

In previous parts of this series, emphasis was given The fast-machining steels must then be carburized
to troubleshooting of the sequences for pre-plating or case-hardened to obtain a surface with the hardness
and electroplating over metals, Parts 1 and 2;1 required to support the top chromium electroplate.
the causes, symptoms and troubleshooting for Case hardening is the generic term covering several
pores, pits, stains, blistering and “spotting-out” processes applicable to steel or ferrous alloys. It changes
phenomena, Part 3;2 and troubleshooting plating on the surface composition of the top layer, or case, by
plastic systems, Part 4.3 Here in Part 5, causes and adsorption of carbon, nitrogen or a mixture of the two.
some typical examples of problems that occur in By diffusion, a concentration gradient is created. The
electroplating as a result of a) thermal, mechanical heat-treatments and the composition of the steel are
surface treatments, b) the metallurgy of the part to additional variables that should be addressed and taken
be plated or c) effects of plating bath temperature into account in the electroplating procedure.
on plating variables and quality of the deposits When discussing the effect of heat-treatment on
are discussed. subsequent electroplating processes it is necessary to
zero in on the type of heat-treatment involved. We
Nearly every plater has at one time or another had the can define the heat-treatment process as changing the
experience of trying to plate parts that simply would characteristics of the parts by heating above a certain
not plate. The usual assumption is that the parts are temperature and quenching it in a suitable media,
not clean. If parts pass a water-break test, conventional generally water or oil. A secondary process is then
wisdom then suggests that the likely cause is that one used to achieve the desired hardness range. This type
or more solutions are not as they should be. After all, of heat-treatment, commonly called neutral hardening
if the parts cannot be properly plated it is the plater’s or through hardening, depending on the alloying
fault, right? Wrong! characteristics in the steel or its properties, gives platers
The plater is often the scapegoat even if the problem few problems since the surface has not been chemically
is caused by the condition of the basis metal before the changed to any significant degree.
part enters the first plating solution. Some problems Most heat-treatment problems occur when the
cannot be completely prevented by the best solutions surface of a material is changed to achieve certain,
and the finest techniques currently known to the prescribed characteristics. There are a few ways of
electroplating industry. Often the most difficult doing this:
problems for the plater to solve come from heat-treating,
polishing and buffing or barrel finishing operations. 1. In nitriding, the part is subjected to nascent nitrogen
Nevertheless, it is important for the plater to be able to and the nitrogen is absorbed into the surface of
identify these problems correctly, if for no other the solid ferrous alloy to obtain defined hardness
reason than to protect his or her own interests. In characteristics. Quenching is not needed to produce
some cases the defects can be solved by suitable a hard case.
pretreatment, if the plater identifies what is causing 2. In carbonizing, the part is exposed at a high
the particular problem. temperature to a source of carbon that is absorbed
into the skin of the part surface.
Influence of Heat Treatment & Mechanical 3. Carbonitriding is a case-hardening process in which
Preparations a suitable ferrous material is heated above the lower
Heat Treatment transformation temperature in a gaseous atmosphere
Steel is frequently plated with functional chromium of such composition as to cause simultaneous
or sometimes with hard nickel for improved wear absorption of carbon and nitrogen by the surface and
resistance. It is vital that the substrate be hard enough by diffusion create a concentration gradient. Cooling
to withstand the pressure that will be applied to the top at a rate that produces the desired properties in the
chromium electrodeposit. If this substrate is too soft, it workpiece completes the heat-treating process. This
may “cave-in,” causing failure of both the electroplated process seems to give platers the greatest amount
deposit and the part. One way to get a surface hard of difficulty. The hardness is relatively shallow. The
enough for such applications is to use deep-hardening penetration generally is less than 500 µm (0.020 in.)
steels that are heat-treated to produce the desired and in commercial practice, it generally is 75–250
mechanical properties. This would be no problem if µm (0.003-0.010 in.) deep. It produces a very hard,
only a few parts are required. Where the application abrasion-resistant surface, while preserving the
requires large numbers of parts, fast-machining soft ductility of the core.
steels are generally preferred.
4. Decarburizing is a loss of carbon on the surface layer of washing. They will plate readily after a simple, anodic
the carbon containing steel. It occurs by the reaction of alkaline electrocleaning.
carbon with one or more chemical substances from the What if conditions are not ideal? If there are leaks in the
medium that contacts the surface. The process is another furnace or in the lines feeding the furnace, soot may be
source of trouble for the suspecting or unsuspecting deposited. This can range from a faint trace to a heavy layer.
plater. Heat-treating case-hardened parts that are to be Anodic electrocleaning will not remove the soot, causing
hard chromium plated, for instance, may decarburize serious problems in subsequent electroplating steps. Fine
the surface. When chromium is plated on this surface, a shot blasting, glass beading, vapor honing or grinding is
three-layer structure results. The underlayer is hardened necessary to salvage such parts. Again, this is a costly
steel, the middle is the decarburized surface and the additional step that should be avoided.
overlayer is hard chromium. The decarburized surface All platers are discontent with the presence of soot, smut,
is rather soft, and the hard chromium will not take the heavy oxides, greases or oil that have been baked on the part
load nor will it have good adhesion. Poor adhesion is a during heat-treatment. When parts are adequately cleaned
general problem with all steel that has been decarburized. before they go into the heat-treat furnace, the plater’s job is
Problems also arise when the decarburized layer is rather definitely made easier. One way to accomplish this, wherever
thick [500 – 750 µm (0.020-0.030 in.)] and 125 µm (0.005 possible, is to make the heat-treat foreman the supervisor
in.) is removed in the grinding step to obtain a sound of the electroplating department as well. This may often
clean surface. The ground surface appears smooth and be impractical and there will always be some baked-on
plates properly, but the resultant product often does not soils to be removed.
have good physical properties. Cleaning such parts in a solvent degreaser is not the
best practice. It removes, by dehydration, the last trace of
In hard chromium electroplating the surface metallurgy anything that could be solubilized, making cleaning more
of the steel is rather important, if not the most important difficult. It is preferable to use a solvent emulsion cleaner
parameter. Change in electrical resistance is an example of as the first cleaning step.
properties, which are influenced by metallurgical factors. Oxides on heat-treated parts are also a source of problems.
Electrical resistance changes with the carbon content of the They are nearly always the result of improper furnace
steel. Data from the literature4 shows that pure iron has a operation. Removal of an oxide film requires careful
resistance of 10 µΩ•cm; steel, a mixture of pure iron and techniques to avoid damaging the parts.
carbon, has a resistance of 16 µΩ•cm. The amount of current At times it is difficult to nickel plate a nitrided surface and
required in electroplating varies with electrical resistance. cover it properly. Nitriding has an effect similar to that of a
Hardening of steel causes a marked change in resistance. fine sand blasting. The effective area of this mildly rougher
Heating above the critical temperature and quenching raises surface may be larger than the visual area by a factor of
the resistance from 16 µΩ•cm to 46 µΩ•cm. Obviously two or three. In addition, the surface becomes more difficult
the carbon content of steel is an important variable in to clean. In the pickling or acid treatment steps, with this
electroplating. larger effective surface area, there is more acid attack and
Since hardening is often necessary, and given that the a tendency to leave an insoluble smut on the surface. This
resistance is noticeably changed as a result, subsequent in turn leads to poor metal coverage and poor adhesion in
processing must take into account these changes. Current subsequent electroplating.
density can be increased or other appropriate changes made Proper pretreatment of a nitrided surface uses mechanical
that can improve throwing power to compensate for the cleaning methods. In chemical cleaning steps, some scrubbing
increased resistance. Compensating for other changes caused or mechanical action is desirable, e.g., tumbling the parts
by heat-treating, is unfortunately not quite so simple. in cleaning solution. Strong acids must be avoided, as they
Perhaps the best example of the other variables introduced will form a weak, brittle surface that will not properly
by heat-treating is scaling. Parts heat-treated without a proper plate or not plate at all.
protective atmosphere are oxidized and scaled. The common In producing a carbonitrided case on steel parts, it is
practice of reverse-current (anodic) electrocleaning will not possible that cyanide may concentrate in localized spots
remove this type of surface contamination, and parts cannot on the part surface producing a solid nitride. Plating these
be correctly plated in this condition. spots is difficult. The usual pickling procedure for such
Additional mechanical cleaning such as shot blasting, parts is a double-alkaline anodic electrocleaner followed
vapor honing, glass beading or grinding may be necessary by a 50-percent hydrochloric acid pickle. Overpickling
to salvage such parts. Mechanical finishing is an additional must be avoided. In practice, a properly applied 50-percent
expense, and it is cheaper to avoid the scaling rather than hydrochloric acid should not cause overpickling. The problem
to correct it later with further processing. The surface can with spots can be solved either by using a cyanide copper
be protected and oxidation prevented in one of two ways. strike, or a low-pH nickel strike (pH 2.0) and enough initial
The part can be heat-treated in a molten salt bath, or in a surge current to initiate nickel plating. The parts could then
controlled-atmosphere furnace. be transferred into a bright nickel bath.
Controlled-atmosphere furnaces are more widely used. Surface stresses induced in heat-treating can also affect
Passing a mixture of natural gas and air over a hot catalyst subsequent electroplating. For instance, when socket
generates these atmospheres. This produces an atmosphere wrenches are hardened before nickel electroplating, the
of carbon monoxide, hydrogen and nitrogen. Natural gas surface stresses in the steel will lead to stresses in the
can be added in the furnace to increase the carburizing nickel deposit. These stresses are much greater than normal
potential. Adding ammonia increases corrosion resistance in bright nickel deposits. Such highly stressed nickel
and hardness. plate can crack.
Under ideal conditions, the controlled-atmosphere furnace Yet other parts being plated in the same system, even ones
delivers parts that have a clean, dove-gray color after that might be plated and then formed, may not be cracking.
One may be tempted to blame the cracking on “brittle nickel,” The techniques used in removing scratches from a surface
but the real cause of this stress is the epitaxial tendency of are also important. Previous research5 on the buffing of
electrodeposits to match the structure of the basis material. zinc and aluminum die-castings has shown this. Different
The first few millionths of an inch, perhaps no more than sized scratches were scribed and the wheel work necessary
the first 50 millionths, of an electrodeposit tends to match to remove those scratches was measured. Aluminum was
the crystal structure of the surface being plated upon. This buffed with a surface speed above 7,000 ft/min. It was found
becomes troublesome if that surface is stressed. that the scratch still remained on the surface and was 2½
In electroforming, this problem is often easily identified. times wider than originally. It was found that, at such a high
When using a low-stress nickel bath (e.g., sulfamate) to speed, the wheel came to ride atop the V-groove. The wheel
plate nickel on a hardened mandrel that has high surface widened the groove, instead of getting to the bottom of
stresses, one will find that the deposited nickel has high it and flattening or removing it. Clearly, proper polishing
stress that causes difficulties. and buffing techniques are of major importance in proper
scratch or pit removal.
Mechanical Preparation
Buffing and burnishing may cause problems that are even Field Examples
more difficult to detect and correct. During buffing operations, Careful selection of buffing compounds and cleaners is
surface can be smeared in such a way that imperfections are important. Some cleaners just do not chemically attack
hidden. The parts will appear fine immediately after buffing, certain materials that are used in the polishing and buffing
but after cleaning and acid treatment, the flaws will show. compounds. If the plating plant does its own buffing and
By this time, however, it is too late. The parts are on their polishing, one can make sure that cleaner and the compound
way through the plating cycle and the defective surfaces are are compatible. If on the other hand, the polishing and
being plated. In burnishing, there is a tendency to produce buffing is outsourced, one may want to investigate the
hammered-over corners and edges. The metal is actually polishing and buffing compounds being used on a job
folded over and seams are present, resembling a lap joint. that is particularly difficult to clean, and make necessary
Such parts are hard to rinse and it is difficult to produce good accommodations.
plating on such a surface. An example of one of the more difficult cleaning jobs
involved plating a strip of steel that was finished flat. The
Grinding Slivers final polishing operation was carried out with a 240-grit
When present on the metal surface, grinding slivers can belt to produce a satin finish. However, it was impossible
cause acute problems. In hard chromium plating, the slivers to obtain a smooth plated finish no matter what was tried.
can be pulled up from the basis metal by the highly-stressed High leveling nickel did not eliminate the roughness, nor
top chromium layer. If slivers are present on the surface and did leveling copper. Filtering the bath did not help either.
a stressed electrodeposit is applied, the slivers will be raised Finally the search for problems was focused toward cleaning
to cause roughness and bumps. Probably 15-25 percent of all of the basis metal. The cleaning operation turned out to
ground surfaces that are hard chromium plated have grinding be the problem.
slivers remaining that can lead to this kind of roughness. The reason for poor cleaning was that the metal was
This type of roughness will not be hidden until the parts are magnetized. The polishing department held the strip flat
plated with as much as 500 µm (0.020 in.) of chromium. The during belt polishing with magnets underneath. Each part
weak leveling ability of the chromium bath is not adequate that was polished became magnetized. Anyone who has
to compensate for this effect. ever tried to remove polishing dust from magnetic steel, can
One possible solution to this problem is electropolishing. imagine how hopeless it was going through cleaners and
If the sliver problem is extended to a depth of 25 µm (0.001 acid pickle with the intent of getting an absolutely clean
in.), this affected zone could be removed. Of course, the part surface. Using a simple demagnetizer,6 the parts were
or plating specification may not permit the removal of 0.001 passed through a magnetic field that removed residual
in. from the surface. In hard chromium, it may be either magnetism. After that, it was rather straightforward to
too difficult or too costly to plate an extra thousandth when clean the part.
0.005-0.006 in. are already called for. Many platers choose to The same thing can happen with parts that are horizontally
ignore grinding slivers, to their later dismay. ground on a magnetic chuck, or that have been lifted by a
magnet. Occasionally, this problem can happen in a barrel,
Polishing Slivers where the parts have simply run up a track with a magnetic
These can also cause problems. For example, pits in a deposit carrier or where the parts have been picked up in bulk with
from an acid copper bath have been traced to polishing an electromagnet. Particles that are magnetically attracted
slivers. The typical pit had a “fish tail” appearance. After can be in the form of chips, powders and oxides. These
cross sectioning and looking at it under the microscope, the contaminants will adhere to magnetized parts during the
culprit was found to be a polishing sliver from a 140-grit cleaning operation and then show up as roughness after
belt. The cyanide copper strike did not fully cover the entire electroplating.
sliver. Further, a surface streaking formed in this area, which Another example is a case where the basis metal was
resembled a typical gas-plating pit. Instead, it was caused by unfairly blamed. Cross-sectioning of particular die-castings
a micron-size metal sliver. revealed the presence of chill shot in the casting at every
spot where there were blisters in the electroplated deposit.
Grinding Burns The manufacturer was considering the purchase of a new
These are difficult to recognize. Sometimes grinding wheels die caster to obtain better quality castings. Then the logical
or belt polishers are operated in a way that will leave powdered question was raised. How had these parts been plated
metal or a heat-checkered surface. Obviously this is not a previously with no trouble? Further inquiry found that the
satisfactory surface for hard chromium plating. change had been made from previous practice.
 When electroplating these porous die-castings, in order to installation. It therefore must be obtained experimentally or
increase the throwing power, the free cyanide in the copper semi-empirically. In general, the resistivity of most aqueous
strike was reduced to about 2.0 g/L (0.3 oz/gal), from the solutions decreases by about 2 percent for each increase
usual 11.0 g/L (1.5 oz/gal). With porous castings, extensive of 1ºC or 1 percent for each increase of 1ºF. Therefore, a
gassing in a highly inefficient cyanide copper bath caused the lower voltage is required to produce the same current density
trouble. The pores filled with hydrogen, which would later at the same temperature.
expand and escape, causing the blisters.3 In the case of alloy deposition, an increase in temperature
The obvious question is how to recognize some of these affects:
problems caused by the condition of the basis metal. In job
shops, one should be suspicious any time one particular (a) the partial polarization curves of alloying metals (the
job among others is running into trouble. A jobshop has deposition potential of metals usually becomes more
an advantage because it is plating a variety of work and noble with higher temperatures),
can isolate and focus attention on a particular job that (b) the respective cathode efficiencies, and
is causing trouble. (c) the tendency of the metals to form an alloy.

Influence of Temperature on Plating Bath Performance In general, increased temperature aids the deposition of the
The magnitude and control of temperature is a critical variable more noble metal. It has same effect as agitation. For example,
in all plating baths, and it is essential for the consistent it increases the proportion of copper in brass electrodeposits.
performance of any deposition bath. For best results, it must However, the effect is actually more complicated since
be controlled within ± 1ºC from the optimum. temperature changes may alter the degree of dissociation of
Unsuspected temperature fluctuations, appreciable, but the metal complexes and have various effects on polarization
not appreciated, can occur when the electroplating baths factors.
are operated with faulty or marginal heating and/or cooling A number of other relevant factors are involved in
equipment. Too wide a temperature range can have a connection with the effect of temperature on the plating
considerable influence both on the operating conditions baths:
of the bath and on the structure of the deposit. At low
temperatures, the deposits will tend to become brittle and • The crystal structure will be coarser when the temperature
it will be found difficult to operate at the normal current is raised without changing any of the other electroplating
densities, as edge burning will occur. conditions. As a consequence, to obtain the same fine-
In general, it is possible to apply higher current densities grained structure at the higher temperature it is necessary
in hot as opposed to cooler plating baths. The advantages of to increase the applied current density.
higher operating temperatures are interrelated with several • The deposit hardness usually falls with an increase
factors, such as: in temperature.
• Temperature clearly affects the hydrogen content of the
(a) higher solubility of basic plating bath components (with deposit. In a very early study,8 for the metals of iron
some exceptions), group, an increase in solution temperature from 1ºC to
(b) higher ionic mobility and therefore increased bath 75ºC caused a marked reduction of the hydrogen content.
conductivity that allows the use of higher current For sulfate-based nickel-plating bath, an increase in
densities, from 20ºC to 63ºC decreased the hydrogen content to
(c) in most baths, reduced anodic and cathodic polarization 1/3 of its original value.9
(e.g., nickel baths), • Cathodic reactions are influenced by temperature
(d) increased cathode current efficiency (a notable exception fluctuations. For example, in an acid zinc bath, the
is chromium baths), variation of the hydrogen overvoltage leads to coarser
(e) improved anode corrosion, deposits that also cover the surface more irregularly than
(f) the ability to operate more dilute baths without loss when the bath is worked at a higher temperature. In the
of performance, and case of nickel baths, the complex cathodic reactions give
(g) reduced power consumption due to lower voltage needed. rise to basic products (hydroxides and oxyhydroxides)
that can be occluded in the deposit and modify the
However, as a trade-off there are possible disadvantages properties of the plated metal. Temperature is one of
to higher solution temperatures, such as: the factors that modify these reactions. Below 30ºC, the
nickel deposit tends to break into small hard patches that
(a) an increased tendency for hydrolysis and precipitation poorly adhere to the basis metal (“burning”). On the other
(e.g., metallic impurities in nickel, iron or zinc baths, hand, at 55 - 60ºC, the deposits are more ductile and softer
leading to pitting), and have less tendency toward flaking.
(b) an increased tendency to decompose organic brightening • The dependence of throwing power on temperature is
and leveling agents, a rather complex phenomenon. It is the result of two
(c) production of passive deposits that will need additional opposing influences. The temperature rise serves to
activation,7 increase the bath conductivity. In addition, by facilitating
(d) reduced throwing power, the diffusion of the ions, it reduces the cathodic
(e) excessive evaporation that can lead to notable changes in polarization. According to whether the first or the second
bath composition and/or difficulties in rinsing, and of these phenomena is the dominant influence, the
(f) shortened plating equipment life. throwing power is either increased or reduced. Often
these effects will cancel each other out. In nickel baths,
These two opposing sets of factors make it difficult to therefore, the variation of the throwing power with
predict the best temperature for any given bath at a given temperature will also depend on the pH value. The
 variation is not noticeable when the pH is high enough, Acknowledgement
but it is quite significant with a lower pH bath. In the The author is indebted to Simon Gary for his contribution.
case of chromium baths, the throwing power will be
better around 35ºC than towards 55ºC.
References
• Electrodeposits obtained from electrolytes operating
1. N.V. Mandich, & W. Saas, Plating & Surface Finishing,
at higher temperatures, have as a rule, lower internal
87, 121 (June 2000); Plating & Surface Finishing,
stresses.
87, 63 (July 2000).
2. N.V. Mandich, Plating & Surface Finishing, 87, 74
Temperature changes in the plating bath will most often
(December 2000).
necessitate modification of other bath factors to obtain
3. N.V. Mandich & D.W. Baudrand, Plating & Surface
a balanced working result. Therefore, increasing the
Finishing, 88 (September 2001).
temperature will allow higher salt concentrations to be used,
4. Handbook of Chemistry & Physics, 73rd Edition, CRC
which in turn allow higher current densities and consequently
Press, New York, NY (1995); p.12-121
higher plating speeds. Other factors must also be modified.
5. Mechanical Finishing of Metal Surfaces, AES Research
For this reason, higher temperature operation in a nickel bath
Report, Serial No. 56, Project No. 18, Ser.No 56, AESF,
requires that the pH and the concentration of the boric
Orlando, FL (1967).
acid and metal salts be modified. In a chromium bath, the
6. S. Modjeska, Product Finishing, 44 (May 1965).
content of chromic acid must be increased to accommodate
7. N.V. Mandich, Plating & Surface Finishing, 85, 91
higher temperatures. With alkaline zinc baths, increased
(1998).
temperatures require changes in the values of hydroxide
8. F. Foster, Electrochemistry of Aqueous Solutions,
and free cyanide.
Leipzig (1922).
In general, with bright plating baths, the temperature
9. A.T. Vagramyan & Z.A. Soloveva, Technology of
considerably effects the current density range over which
Electrodeposition, R. Draper, Teddington, UK (1961);
bright deposits are obtained. At lower temperatures, the
p. 193.
bright plating range will be narrower. This renders the bright
10. N.V.Mandich, Proceedings of AESF 86th Annual Technical
plating of deeply recessed and contoured parts rather difficult.
Conference—SUR/FIN® 1999, Cincinnati, OH, AESF,
An irregular blotchy finish may result, some parts of the
Orlando, FL (1999).
surface being brighter than others. Even a dull deposit may
result in places. It is well known, for example, in chromium
plating, that the bright range is much more restricted at 10ºC About the Author
than at 35ºC. This is the reason why totally trouble-free Dr-Ing N.V. Mandich, CEF, AESF Fellow,
operation cannot be easily obtained from a cold chromium is founder, president and research director
bath, at least for decorative plate, regardless of the of HBM Electrochemical Co., Lansing,
noticeable increase in plating speed and some increase IL. He holds a Dipl-Ing degree in
chemical engineering from the University
in the hardness.
of Belgrade, Yugoslavia; a MSc. in
theoretical chemistry from Roosevelt
Controlling & Monitoring Solution Temperature University, Chicago; and a PhD in
In the early days of electroplating, a gas flame was usually applied electrochemical engineering
lit under the tank and that was it. The flame was adjusted by from Aston University, England, under
eye and the temperature detected by touching the solution professor J.K. Dennis. He is an AESF certified instructor and
gingerly with a finger if a thermometer was not available (or a member of the Hard Chromium and Pulse Electrodeposition
the operator was too lazy to use it). Nowadays, temperature is Plating Committees of the AESF. He also belongs to the ECS,
automatically controlled in the plating bath within one degree ISE, and the AAAS and is a Fellow of the IMF. He consults
or better by appropriate sensing and heating devices. and lectures in the U.S. and abroad. He holds 12 U.S. patents
Solution temperature can be maintained with the and patent applications and has more than 100 technical and
thermocouples, thermistors, resistance temperature detectors research papers either published or submitted.
or integrated circuit devices. In addition, many sensors used
for the automatic control of other plating variables (e.g.,
automatic brightener additions, pH, etc.) are temperature-
sensitive and must be temperature-compensated for accurate
measurements.

Conclusions
The problems related to heat-treatment, basis metal
preparation or fluctuations in bath temperature should be
positively identified. Once identified, search for cause is in
order. Once it is established that the problem is related to
heat-treating or basis metal conditions, the preplating process
can be modified and something can be done about it.
After it is recognized where the origin of the problem
lies, one can speculate on why it is there and what best
set of corrective measures can be contemplated and
implemented.10