Академический Документы
Профессиональный Документы
Культура Документы
Surface Preparation
For Electroless Nickel Plating
Juan Hajdu
Another reason for the need of a very careful selection of the preparation
process is that it can significantly affect the porosity of the metal deposit. This is
particularly true for electroless nickel. Residues from cleaners and deoxidizers
can increase the porosity of electroless nickel, creating passive spots that will
not initiate electroless plating (6). Thin (less than 5 pm) electroless nickel
deposits are more porous than electrodeposited nickel of comparable thickness.
During electroless nickel plating, the deposition process initiates at discrete
sites and the substrate will become fully covered through the lateral growth of
these sites. Short plating times will not allow full coverage of the base material,
causing porous electroless deposits.
Iron and its alloys are the most frequently plated substrates. From a surface
preparation standpoint, they can be grouped as low alloy and carbon steels; cast
iron; and high alloy steels. The principles of preparing ferrous surfaces are
based on successive steps for soil removal, deoxidation, and surface activation.
The manner in which these steps are carried out will depend on the type of alloy
processed.
Steel and cast iron parts are cleaned using conventional techniques such as
alkaline cleaning, solvent cleaning, or electrocleaning similar to the processes
used in electroplating or other metal finishing procedures. In somecases, where
the surface has been severely corroded or is covered by scale or other strongly
adherent residues, mechanical pretreatments such as sandblasting, shot
peening, or wheelabrading may be necessary.
Alkaline soak cleaning with commercial cleaners are frequently preferred.
These materials contain a combination of alkaline sodium compounds such as
hydroxide, carbonate, silicates, phosphates, and organic surfactants. The
selection of the cleaner will depend on the nature of the surface contamination
and substrate, and the assistance of the supplier can bevery helpful in achieving
effective and economical cleaning. In some cases, solvent or vapor degreasing
may be used prior to the alkaline cleaning steps. A good summary of cleaning
practices for steel can be found in the ASTM Standard Practices (5).
Carbon and low-alloy steels are deoxidized using either acid pickling
solutions or alkaline deoxidizers. Pickling solutions, in general, use hydrochloric
or sulfuric acids, combinations of these mineral acids, or salts of the acids. On
carbon steels, hydrochloric acid is used at 10 to 50 percent concentration while
sulfuric acid (2 to 10 percent) is also used. Sulfamic acid pickles are
recommended for leaded steels. It is convenient to avoid the use of pickling
inhibitors in this process, since they may interfere in the initiation and activation
necessary for electroless plating.
Alkaline deoxidizers containing organic chelating agents and/or sodium
cyanide are frequently used in surface preparation, since they offer specific
advantages over acid deoxidizers. Alkaline deoxidants will remove oxides
without attacking the substrate metal and are less prone to cause hydrogen
Surface Preparation lor Electroless Nickel Plating 195
Cast Iron
Alkaline clean
Water rinse
Alkaline deoxidizer with periodic reverse current
Water rinse
Electroless nickel plate
After steel and ferrous alloys, aluminum alloys constitute the largest group of
substrates for electroless nickel plating. Electroless nickel imparts hardness,
wear, abrasion resistance, solderability, and corrosion resistance to aluminum
substrates. The preparation of aluminum and its alloys is quite specific to this
metal, since aluminum exposed to air is always covered by a dense oxide coating
that must be removed before the parts can be plated. Furthermore, the
deoxidized parts must be protected during the transfer, to avoid reoxidation of
the highly active aluminum surfaces.
Another characteristic of aluminum is its potential reactivity with electroless
nickel solutions. Most of the phosphorus nickel bathsareacidic, and with nickel
being very positive to aluminum on the electromotive scale, immersion deposits
of nickel and chemical attack of the aluminum substrate will occur, interfering
with the good adhesion of the electroless nickel coating. To protect the
aluminum surfaces during processing, zinc immersion deposits (zincates) are
used. The zinc deposit protects aluminum against reoxidation from atmospheric
exposure and redissolves in the electroless nickel solution, exposing an oxide-
free aluminum substrate, upon which nickel deposits form adherent coatings.
Other methods based on immersion deposits or oxide films (7-9) have been
proposed for this application, but are seldom used in electroless nickel plating.
For this reason, only processes based on zincating will be reviewed here.
Aluminum parts are generally prepared by submitting them to alkaline cleaning,
acid or alkaline etching, deoxidizing (conditioning), and zincating. Cleaning is
done with mild alkaline cleaners that will not attack (or only attack slightly) the
substrate, while still removing superficial organic contaminants. Strongly
alkaline cleaners will aggressively attack aluminum, interfering with appearance
and adhesion of the electroless nickel deposit.
Conditioning is needed to remove alloying elements from the surface and to
prepare it for uniform zincating. This step is generally done by immersion in
strong nitric acid-based solutions. Nitric acid forms a thin, light, uniform oxide
film on aluminum that protects it from further attack by the acid. The
composition of the conditioning solution will depend on the type of alloy being
treated. For pure commercial aluminum and aluminum-magnesium wrought
alloys, simple nitric acid solutions (50 percent by vol.) can be used. For treating
alloys with a higher percentage of metallic constituents, two-step conditioning
processes are used, in which the first step consists of removing interfering
constituents with mineral acids (such as sulfuric or phosphoric acid mixtures) or
alkaline etchants and then treating the parts with 50 percent nitric acid. For
casting alloys that contain a high percentage of silicon, hydrofluoric acid or
fluorides are added to the nitric acid to dissolve silicon.
Zincating was developed originally for the electroplating of aluminum and has
been widely reviewed in technical and patent literature (8,lO-12).The principle
of the process is the formation of an immersion deposit of zinc on the aluminum
surface by displacement from an alkalinezincate solution. The basic formulation
198 ELECTROLESS PLATING
of a zincate bath consists of zinc oxide (50 to 100 g/L) and sodium hydroxide
(250 to 500 g/L). Proprietary zincate solutions contain other ingredients, such as
copper and iron salts and organic chelating agents, to produce more uniform
coatings and to permit the use of lower concentrations of zinc ("dilute zincates").
Many formulations for this type of material can be found in the patent literature
(13,14). Typical formulationsfordilutezincatesolutionscontain5 to l o g ofzinc
oxide and 50 to 120 g/L of sodium hydroxide. Acid zinc immersion systems have
also been reported (16) using zinc sulfate (720 g/L) and hydrofluoric acid (17.5
mL/L) .
The mechanism of zincating and the reaction of the zinc immersion deposits
in the electroless plating bath have been reported in several papers (8,12,15).
The basic mechanism of zincating is the displacement of zinc from an alkaline
zincate solution by aluminum:
w.
C
T
F h
Ia
.-
g
a
.
c
I
w
m
0
0
0
c
is
reduction of nickel (21). Older solutions become more aggressive and give less
adherent nickel coatings, and for this reason, surface preparation procedures
that produce good results with relatively fresh electroless nickel plating baths
may yield nonadherent or blistered deposits as the bath ages. This is the main
reason why electroless nickel baths have a shorter life when used for plating
aluminum than when used on steel. The use of a non-aggressive electroless
nickel strike has been proposed to remedy this problem (22) and extend the
useful life of the electroless plating bath.
While the plating of aluminum may appear too complex for consistent
processing, industry has been very successful in resolving the requirements of
depositing electroless nickel on a broad variety of alloys and satisfying many
end use requirements. Experience is the key to success in the plating of
aluminum and it cannot be substituted by standard pre-established procedures.
The following cycles are presented to illustrate industry practice:
200 ELECTROLESS PLATING
w.
c
?
--..F
c
CD
s
CD
..S
CI
(0
0
0
0
r
i3
Aluminum Castings
Solvent preclean (if necessary)
Water rinse
Surface Preparation for Electroless Nickel Plating 201
As mentioned earlier, copper is one of the metals that will not catalytically initiate
hypophosphite electroless nickel solutions. Copper can initiate aminoborane
and borohydride-reduced baths.
To render copper and copper alloys catalytic, the following approaches are
used in commercial operations:
Soak clean
Rinse
Electroclean anodically
Rinse
Acid dip in 1 to 2 percent HzSOrinse
Activate, using either method 1 or 2 above.
There is a great interest in using magnesium alloys for weight reduction, and
electroless nickel offers good protection for magnesium-based parts. While
used for commercial applications, plating magnesium alloys is not an easy task.
Magnesium is a highly reactive metal and conventional cleaning and deoxidizing
202 ELECTROLESS PLATING
BERYLLIUM
TITANI UM
Titanium surfacesarealwayscovered bya tight oxide film that interferes with the
good bonding of plated metal coatings. The oxide layer must be removed,
preferably by mechanical and chemical attack. The pickling solutions are, in
general, based on nitric and hydrofluoric acids (1,29).
After removing the oxide, the surface is protected by a conversion coating
using fluorides (30),chromates (31), or zinc immersion deposits (1). The most
widely used processes are based on fluoride-containing acid solutions, applied
either by immersion or anodically prior toelectroless nickel plating. It should be
noted that both electroless and electrolytic plating of titanium are plagued by
adhesion problems. A possible cycle could be:
ZINC
At the present time, a number of commercial zinc die casting operations involve
direct plating of electroless nickel for enhanced appearanceand protection. The
Surface Preparation for Electroless Nickel Plating 203
largest single use of electroless nickel-plated zinc die castings is for carburetors
used with alcohol fuel, especially in Brazil.
In many operations, the partsare striked first with electrolytic cyanide copper
prior to electroless nickel plating. The copper strike baths typically contain 20 to
45 g/L cuprous cyanide, 10 to 20 g/L free sodium cyanide, and 15 t o 75 g/L
sodium carbonate. Copper strike baths have the ability to cover complex shapes
and recessed areas when used under the right operating conditions. Most
textbooks on electroplating extensively describe the operation of copper strike
baths and the cleaning of parts prior to copper plating (1,32).
While this approach gives excellent results, there is a continuous interest in
finding a less costly process that requires no electroplating and avoids the use of
cyanide compounds. Several methods have been proposed, and proprietary
materials are available commercially that allow direct electroless plating of zinc
die castings.
NONMETALLIC SUBSTRATES
The main difference between metallic and nonmetallic surfaces resides i n the
nature of the bond between substrate and coating. While adhesion to metal is of
an atomic nature, the adhesion to organic and inorganic substrates is only
mechanical. The basis for obtaining adhesion to these materials is to develop the
right topography on the surface by means of chemical or mechanical treatment.
204 ELECTROLESS PLATING
Nonmetallic surfaces lack catalytic properties and therefore require activating
treatments that will render them catalytic. In general, this activation is done by
seeding the surface with a catalytically active metal.
Parts are plated with the electroless nickel for several reasons. One of the
major uses for electroless nickel is to form a conductive base for electroplating
on plastic or ceramic substrates. Ceramic and glass parts are electroless nickel
plated for bonding or soldering applications. Diamond and other abrasive
particles are encapsulated in electroless nickel for manufacturing plastic-
bonded cutting tools.
The use of electroless nickel for metallizing plastics is discussed in Chapter
14, Plating on Plastics. There are only limited uses of electroless nickel on
plastics for mechanical or decorative applications. A novel application of
electroless nickel is to protect electroless copper deposits used in electronic
devices, such as shields for electromagnetic interference. This application is
also discussed in a separate chapter.
Electroless nickel has been applied extensively to ceramic, glass, and silicon
parts used mainly in the electronics industry. Typical uses are to metallize
conductors, capacitors, transducers, silicon devices, hybrid circuits, and other
electronic components. The processing steps generally include roughening by
chemical attack (if the surface requires it), activating with a catalytic metal, and
then electroless nickel plating. The composition of the chemical etch will
depend on the nature of the substrate. Some typical etch applications are as
follows:
Alumina Ceramics
Soak clean with alkaline cleaner
Rinse
Etch in 25 vol. percent hydrofluoric acid (50 percent) for 5 min at room
temperature
Silicon Devices
Hydrofluoric acid solutions with an addition of ammonium fluoride of Varying
concentration, depending on the type of etch desired, are used in the
metallization of silicon wafers.
Surtace Preparation for Electroless Nickel Plating 205
The roughened parts are rinsed and then rendered catalytic either by the
two-step sensitizing and activating process or by using commercial activators.
Sensitizing is accomplished by immersing the parts in an acid stannous chloride
solution (10 to 100 g/L of SnCIz, 2Hz0), then rinsing and activating with a
solution of palladium chloride (0.1 to 0.5 g/L PdCl in 1 to 3 mL/L HCI).
Commercial activators containing mixed palladium-tin compounds are also
used at 1 to 5 percent dilution. After activation, the parts should be ready for
electroless plating either with hydrophosphite- or amino borane-reduced
electroless nickel solutions. It must be remembered that the final adherence of
the electroless nickel deposit will depend not only on the pretreatment, but also
on the characteristics of the plating process. Aggressive plating baths or
deposits with high internal stresses should be avoided, and thick deposits are
very difficult to produce on this type of substrate.
MASKING
Many parts may require only partial coverage with electroless nickel, and
portions of the substrate must be prctected by masking. Many stop-off materials
(tapes and coatings) used for electroplating can be applied for masking partsfor
electroless plating. Since most electroless nickel solutions operate at high
temperatures, and the parts may stay in the bath for a long time, the masking
materials should be tested thoroughly before using them on expensive parts.
Masking materials may also release organic or metallic contaminants that may
harm the nickel deposits.
A problem commonly encountered when plating small areas in large parts is
how to adjust the plating process to very low surface-to-volume ratios. All
electroless plating solutions will perform best above minimum loading levels,
which may be difficult to reach with masked parts.
REFERENCES