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Plating on Plastics
John J. Kuzmik
The plating of non-conductors has been achieved for many years. Articles
plated were mainly decorative, and adhesion of the plate t o the substrate was
minimal. In the early 1960s' due to technological advances in chemical
processing techniques, plating on plastics began on a commercial level.
Industries that utilize plated plastics include the automotive, plumbing, appliance
and electronics.
One of the early plastics to be plated on a large scale was polypropylene,
which gave adhesion values of over 20 pounds per linear inch. Even though
adhesion was excellent, other problems occurred that ultimately led to the
demise of plating polypropylene. These problems included (1) failure t o pass
thermal cycling due to its high coefficient of linear thermal expansion (i.e., the
amount i n inches per inch the part shrinks in the mold-68 t o 9 5 x lO-'in./in./" c
for polypropylene); (2) brittleness after plating due to notch sensitivity (a
phenomenon whereby a crack in the plate will propagate through a normally
flexible plastic, causing it t o break easily); and (3) "sink" marks caused by the
plastic shrinking i n the mold, especially over bosses and ribs and showing up as
dimples or "sinks" after molding.
Some of the reasons various industries are interested in plating plastics
include (1):
Lowercost
No secondary operations (i.e., no deflashing or buffing)
Design freedom (i.e., the ability to mold large and complex parts)
0 Weight reduction
Weight reduction became a very real benefit to the automotive industry when
the gasoline crunch occurred in the early 1970s.
Many plastics are plated today, including:
0 ABS
Polypropylene
Polysulfone
Polyethersulfone
Polyetherimide
0 Teflon
377
370 ELECTROLESS PLATING
Polyarylether
Polycarbonate
Polyphenylene oxide (modified)
Polyacetal
Urea formaldehyde
Diallyl phthalate
Mineral-reinforced nylon (MRN)
Phenolic
Some typical applications of plated plastics are shown in Figs. 14.1 and 14.2.
Several of the above-mentioned resins have little or no adhesion and/or
unacceptable appearance. Of the resins listed, ABS, acrylonitrile-butadiene-
styrene, has found the widest acceptance in the plating industry. ABS is a
terpolymer thermoplastic that has an acrylonitrile-styrene matrix with butadiene
rubber uniformly distributed in it. This quality makes it unique for plating, as the
butadiene can be selectively etched out of the matrix (Fig. 14.3), leaving
microscopic holes that are used as bonding sites by the electroless plate. Other
factors influencing the choice are:
Lowcost
Low coefficient of thermal expansion
Ease of molding
Good metal adhesion to the substrate
Good appearance after plate
Because ABS is the most widely plated plastic, it will be the material mainly
referred to in this chapter. Scanning electron micrographs of ABS surfaces are
shown in Fig. 14.4.
Quality plating on plastics involves the following three basic steps:
Draft angles should be at least one degree (1") for easy removal of the part
from the mold.
Parting lines (where the mold opens) should be put in a non-significant area
if possible.
Close tolerance fits must include the final plate in the initial part design.
Wall thickness should be sufficient to insure rigidity.
Plate uniformity, which results from current density distribution, must be
considered in the initial design. Use no 90" angles, no V grooves, keep letters
close to the wrface, make angles as large as possible, and crown large flat
surfaces (Figs. 14.5 and 14.6).
380 ELECTROLESS PLATING
Highly polished mold-Poor mold surfaces can cause defects in the molded
part such as pits, which show up in the final plate and cause rejects.
Proper drying of resin-Moisture in the resin can cause "splay" or
delamination on the part, which may result in a blister.
Proper melt temperature-If the melt temperature is too low, stress can be
incorporated in the part, which could cause uneven etching and possible
thermal cycle failure. Consult the resin manufacturer for the proper parameters.
Plating on Plastics 381
i -
Fig. 14.5-Design considerationsfor plating thlckness unlformity: (left) 90” angles and V-grooves
result in poor current distribution; (right) suggested design.
Fig. 14.6-Sharp corners(a) result in poor plating uniformity;(b) rounded corners, both Internal and
external,Improvecoverage. Expansive surfaces (c) should be crowned fora convex surtace as In (d).
Proper mold femperafure-If the mold is too cold, “skinning” can occur,
that is, the first material to hit the mold hardens instantly and the hot material
under it flows, causing a surface skin that may cause delamination.
Proper fill speed-A fast fill speed can overpack a mold, thus making it
harder toetch, resulting in adhesion loss. Best resultsareobtained using a slow
fill speed.
The type of mold release used can have a profound effect on the molded part.
For example, silicon-type mold releases (materials sprayed on the molded
Surfaceto help in the removal of the molded part) should not be used, as they are
extremely difficult to remove and usually lead to adhesion failures (blisters) or
misplate because they hindered the processing solutions from performing their
functions properly. Molders who mold plastic parts for plating generally do not
use a mold release. If it is essential to use one, a stearate or soap type may be
used sparingly.
The addition of fillers (4) to the resin can create problems when plating of the
parts is involved. In some cases fillers are added to the resins to increase
strength (i.e., glass fibers), to impart color (i.e., carbon black or titanium
dioxide), or for fire retardancy (organic phosphates, antimony oxide). In any
case, problems can arise. Glass, for example, usually gives a rough surface to
the finished part. Titanium dioxide can build up in the processing tanks and
cause a rough surface after plating. Some of the fire retardants and other fillers
can leave a non-adherent fiim on the surface that results in no adhesion after
plating. If the film can be removed prior to catalyst, good results are usually
obtained.
Other fillers such as calcium carbonate are added to facilitate etching. These
fillers are preferentially etched out of the surface to create bonding sites
required for adequate adhesion. If these particles are large, a poor surface
results. Generally, a happy medium is reached where adhesion is adequate and
the surface is acceptable. Mineral-reinforced nylon is one such material.
When parts are molded, they are ready to be plated, as there is no secondary
operation required. Parts are racked and run through the processing solutions,
which include cleaners and/or predips, etching, neutralization, preactivation,
activation, acceleration, and finally electroless plating (see Fig. 14.7). These
steps are known as the preplate cycle (5).
CLEANERS
Cleaners are used for removing light soils such as fingerprints, dirt, and other
debris from the parts. They are usually mild alkaline cleaners. In some cases, a
highly wetted chromic acid solution may be used to insure complete wetting of a
part in knurled or lettered areas prior to etching. This will minimize pinpoint
skips in these areas. Cleaning prior to etching is optional and generally not used
if parts are reasonably clean.
Troubleshooting these materials usually only involves chemical analysis to
insure they are up to concentration.
PREDIPS
first use is to help improve the surface of a normally plated but poorly molded,
highly stressed part. This is done on ABS and its alloys by slightly swelling the
surface, allowing the etchant to more uniformly attack the surface. By using a
predip, non-uniform etch conditions are reduced on a stressed part, giving
better overall adhesion. As stated earlier, proper molding can eliminate stress as
well as the need for a predip in the above case.
The second use of predips is to attack or swell the surface of normally hard to
etch plastics. These materials include polypropylene, polycarbonate, poly-
sulfone, and others. This swelling action of the predip enables the chemical
etchant to readily attack the surface of the normally resistant resin. Generally, a
different solvent is needed for each resin in order to be successful.
Troubleshooting the predips involves analysis to insure proper balance.
ETCHANTS
Etchants are usually strong oxidizing solutions that eat away the plastic Surface
to varying degrees, accomplishing two purposes. First, the surface area is
greatly increased, making the part turn from a hydrophobic (water-hating) to a
hydrophilic (water-loving) material. Second, the microscopic holes left in the
surface of the plastic by the etchant provide the bonding sites for the deposited
metal. These sites are needed for adhesion between the plastic and the metal.
When ABS is exposed to an etchant, the butadiene is selectively removed, thus
leaving small holes or bonding sites. Commonly used etchants for ABS are:
This is the ”all chrome” version, which tends to give a finer, more uniform etch.
Both types are used in production. All-chrome etchants require several
milliliters of sulfuric acid per liter of etchant to retard tank deterioration if
chemical lead is used. It is also desirable to have about 40 g/L trivalent chromium
in a new all-chrome bath to avoid over-etching the ABS surface. Etchants are
generally operated at 140 to 160” F for 4 to 10 minutes on ABS. Other plastics
may require higher or lower temperatures and times. Polycarbonate, for
example, uses an etchant at 170” F for 10 minutes, while mineral-reinforced
nylon (MRN) uses one at 105” F for 2 minutes.
As the chrome-based etchants are used, the following reduction reaction
occurs as the plastic is attacked:
Decant part or all of the etchant and rebuild it. This method may cause a
waste disposal problem if provisions for the spent material are not made.
The excess trivalent chrome can be electrolytically regenerated. This can
be accomplished by using porous pots containing an electrolyte of 10 to 50
percent byvol HrSO,. Copper or stainless steel cathodes are then inserted in the
pots. The tank or lead straps may be used as the anode. The usual anode to
cathode ratio is 2:l.The voltage used is 9 to 12 Vat a temperature of 100 to 155”
F. The current is 100 to 150 amps for a 15-cm-diameter by 45-cm-long porous
pot. Efficiency of this regeneration process is best when more than 20 g/L of
trivalent chromium are present in the bath. The reaction involved is:
at the anode.
Using this method and a flash evaporator for the rinses results in a tight closed
loop system. One problem with this system is that all impurities in the etch such
as dissolved metals and titanium dioxide filler are returned to it. This causes a
build-up of impurities that eventually results in problems such as “stardusting,” a
fine roughness usually occurring on the shelf of a part.
The etchant is the most critical step in obtaining an acceptable finished part.
An underetched part can result in poor adhesion and possible skip plate.
Overetching a part can degrade the surface causing poor adhesion and
cosmetics.
Some problems that may be encountered are shown in Table 14.1.
Plating on Plastics 385
Table 14.1
Troubleshooting Etchants for Electroless Nickel
NEUTRALIZERS
After etching, the parts are thoroughly rinsed in water and then put into a
neutralizer. These are materials such as sodium bisulfite or any of the
proprietary products available that are designed to eliminate excess etchant
from the parts and racks, usually by chemical reduction. Hexavalent chromium
( C P ) is harmful in the ensuing steps. Even with excellent rinsing, etchant may
be trapped in blind holes. If this is not rinsed out or reduced to trivalent
chromium (Cri3), “skip plate” can occur as a result of “bleedout” of etchant in
subsequent steps.
Neutralizers are generally cheap to make up and are usually dumped and
remade on a regular basis. They are usually run at 70 to 110” F for 1 to 3 minutes
with air agitation. Troubleshooting is relatively simple, as seen in Table 14.2.
386 ELECTROLESS PLATING
Table 14.2
Troubleshooting Neutralizers for Electroless Nickel
PREACTIVATORS
ACTIVATORS
Activators or catalysts, as they are sometimes called, are materials that in most
cases contain some precious metal such as palladium, platinum or gold.
The early version of activation was a two-step procedure. Step 1 was a
stannous chloride/hydrochloric acid solution in which the stannous ion (Sn")
was adsorbed onto the surface. The part was then rinsed well. Step 2 was a
palladium chloride/hydrochloric acid solution which, when the part with the
stannous ion was immersed in it, caused the Pdt22 ion to be reduced to Pd"
according to the following reaction:
Table 14.3
Troubleshooting Preactivators for Electroless Nickel
The Pd sites formed the catalytic surface needed to deposit the chemical
nickel. Present day catalysts are essentially the earlier two step version
combined. In other words, the palladium chloride, stannous chloride and
hydrochloric acid are in one solution. What we get is a palladium-tin hydrosol,
which is a solution of complex ions and colloidal particles whose activity and
stability depend on the chloride and stannous ion concentrations (6,7).
A typical working activator bath today would consist of the following:
The chloride ion may be maintained with hydrochloric acid or sodium chloride.
When processing a part, the first noticeable change will be evident after the
activator. The part acquires a tan to brownish color. This coloration, unless the
part is black, can easily be seen and is an indication the activator isworking. The
absence of a coloring on the part usually indicates a problem that can result in
skip plate and possibly low adhesion.
The primary purpose of activators is to provide catalytic sites on the plastic
surface. The usual operating conditions for the activator bath are 80 to 95" F for 2
to 5 minutes. Because this is the most expensive bath in the system, care is taken
to analyze regularly. Even when the bath is not being used, analysis for tin is
required, as tin is continually oxidized to the stannic ion (Sn")). When almost all
the stannous is oxidized, the bath "falls out".
Troubleshooting tips for the bath are given in Table 14.4.
388 ELECTROLESS PLATINQ
~~ ~~
Table 14.4
Troubleshooting Activators for Electroless Nickel
ACCELERATORS
rack tips. These contaminants, such as hexavalent chromium, iron, and other
metals, can cause the accelerator to become over-aggressive. This causes the
accelerator to remove not only the stannous tin, but also palladium. When this
occurs, skip plate can be the result. Some materials are designed to minimize the
effect of these contaminants.
Accelerators are usually run at 110 to 140" F for 2 to 5 minutes. Some
problems that may occur are as shown in Table 14.5.
Table 14.5
Troubleshooting Accelerators for Electroless Nickel
ELECTROLESS PLATING
After rinsing, the parts are put into the final step in the preplate cycle. This is the
electroless bath, which deposits a thin, adherent metallic film, usually copper or
nickel, on the plastic surface by chemical reduction. This is accomplished by
using a semi-stable solution containing a metal salt, a reducer, a complexor for
the metal, a stabilizer and a buffer system. When idle, the baths are stable, but
390 ELECTROLESS PLATING
Table 14.6
Troubleshooting Electroless Nickel Plating Baths
solution. Normally 0.0003 to 0.0008 in. of semi-bright nickel are plated, followed
by an electrolytic bright nickel plating solution, which will deposit about 0.0002
to 0.0004 in. of metal. The deposit from the latter bath is generally very specular.
For the best corrosion resistance, a layer of about 0.0001 in. of microporous
nickel can be electrolytically deposited on the bright nickel, followed by an
electrolytic chromium deposit from either a hexavalent or trivalent bath. This
layer,onlyabout5to 10millionthsofan inch thick, isthefinalstepinproducinga
finished part. Be aware that if the surface of the substrate is pitted, scratched,
dented, or marred in any way, electroplating will enhance these blemishes. Care
must be taken when handling and racking plastic parts to avoid damaging them
(1). Parts are usually plated to meet various service conditions, which are:
Table 14.7
Troubleshooting Electroless Copper Platlng Baths
The various plate thicknesses required for each type of service are given in
Table 14.8.
Chromium is not theonlyfinish that can beapplied to plated plastics. Once the
electroless is put down, any plate combination can be used. Final finishes can be
brass, gold,, silver. or any of the other finishes put on plated metal articles.
After plating to thedesired specification, most platers perform quality control
testing on plated parts. These tests include:
Table 14.8
Minimum Plating Thickness Requirements
Under Various Service Conditions
Total
Service Copper nickel Chromium
SCl 0 6 mils -03 mils 10 pin
sc2 0 fi mils 0 6 mils 10 pin
sc3 0 6 mils 0 9 mils 10 Uin
sc4 0 6 mils 1 2 mils 10 p i n
Thermal Cycling
Because various plastics have various coefficients of thermal expansion, some
do not readily pass this test, even though adhesion is good. To counteract this,
more copper may be plated on the part to act as a cushion.
I n thermal cycling, the part is first put into an air-circulating oven for 1 hr at
180" F. The part is then removed and held at room temperature for 15 min. The
part is then placed into a cold chamber at -20' F for 1 hr. This is repeated a
minimum of three times. Loss of adhesion, blisters, or cracking indicate a failure.
Part design and molding can also affect thermal cycling. This test was designed
for ABS and does not necessarily apply to other substrates.
C.A.S.S.
The C.A.S.S. ( l o ) , or Copper Accelerated Acetic Acid Salt Spray Test, checks
the corrosion resistance of the final plate. This test is generally performed in a
cabinet, according to ASTM 6-368. Requirements are as follows:
SC1-None
SC2-1 8-hr cycle
SC3--2 16-hr cycles
SC4-3 16-hr cycles
N.S.S. (10)-5 percent neutral salt spray, which is also used in another
corrosion test-ASTM 6-1 17.
Plate thickness-Checking plate thicknesses by either a destructive or
non-destructive method.
Outdoor exposure-Setting industrial samples in environments they will be
normally exposed to.
394 ELECTROLESS PLATING
C.S.A. 8-125, LRP-15 (11)-A Canadian test for plumbing goods that
includes 450 cycles of dipping the parts in alternating hot (175' F) and ambient
(70' F) water baths for 40 seconds. One cycle is 40 seconds in the hot water, and
40 seconds in the ambient water.
0 Airplanes
0 Computers
0 Electric motors
Ignition systems
0 Power lines
0 Radio and television transmitters
0 Videogames
0 Lightning
copper and/or nickel. The process used would be similar to that presently used
to plate on plastics. Steps would include:
6. Rinse
7. Preactivate (if necessary)
8. Rinse
9. Activate
10. Rinse
11. Accelerate
12. Rinse
13. Electroless copper
14. Rinse
15. Activate
16. Rinse
17. Electroless nickel
18. Rinse
19. Dry
Table 14.9
EM1 Shielding Effectiveness
Shielding
Attenuation effectiveness
0 to 10 dB Very little
10 to 30 dB Minimal
30 to 60 dB Average
60 to 90 dB Above average
90 to 120 dB and above Maximurntostate-of-the-art
Table 14.10
Coating Techniques for EM1 Shielding
Of Plastic Housing
Method Advantages Disadvantages
Zinc arc spray Good conductivity Need special equipment
Hard, dense coat Adhesive problems
Effective over a wide Coating cracks
frequency range May distort the housing
Conductive painfs
Silver Good conductivity Expensive
Conventional equipment
Resists flaking
Conductive oxide
Easy to apply
Nickel Conventional equipment Multiple coats needed for
good conductivity
Resists flaking Thickness problems
Economical Questionable attenuation
Easy to apply
Copper Conventional equipment Multiple coats needed for
good conductivity
Resists flaking Thickness problems
Economical Oxidation reduces
Easy to apply conductivity
Vacuum metallizing Good adhesion Size limited to vacuum
Good for all plastics chamber
Not limited to simple Base coat needed
designs Expensive special
Familiar technology equipment
Low thickness
Cathode sputtering Good conductivity Expensive equipment
Good adhesion Microscopic cracking
May distort housing
High power needed
Foil application Die cut to part shape Complex parts are difficult
Good conductivity to coat
Good for experimentation Labor intensive
Conductive plastics No secondary operation Material expensive
Poor attenuation
Surface usually poor
Silver reduction Good conductivity Tendency to oxidize
Low initial cost Difficult to mask
Multiple-step process
Electroless plating (copper Uniform thickness Limited to Lertain resins
and/or nickel) Good for all size and shape
parts
Good conductivity
Resists chipping
Can be electroplated for
metallic appearance
Can be painted
Plating on Plastrcs 399
REFERENCES