The Evolution of a Process: Fifty Years of

Electroless Nickel
-F?F5%0
N.V. Mandich, zp2.y
HBM Electrochemical & Engineering Co., Lansing, Ill.
and G. A. Krulik, /w
Applied Electroless Concepts, El Toro, Calif.

E. lectroless nickel plating is a rela-

hvely new technological process.
The first laboratory experiments were
troless plating are conceptually closely
related.
Despite the difference in techniques
Table 1. Substrates for Electroless
Nickel Coating
Metals
done in 1944 by A. Brenner and G. among the hasic categories, the same Stainless steels
Riddelll during World War 11. Public types of coatings can he obtained from High strength steels
announcements were made a few years each process, whether it be nickel, Mild steels
later. This work bad been done without nickel-phosphorus or other alloys; for Aluminum
knowledge of the earlier observations example, a nickel-phosphorus coating Zinc
by Roux in 1916* and by Wurtz3 in Copper
can be made by thermal decomposition Exotic metals and alloys
1845. The early work was not success- of nickel carbonyl and a phosphine:
ful due to poor quality reagents and electrolysis of a nickel solution con- Bulk Dielectrics
other factors. Thus, Brenner and Rid- taining hypophosphite? or by elec- Plastics
del are credited as the discoverers of troless deposition?-* These coatings Ceramics
Glass
this technology, as they developed the may be the same by hulk chemical Fabrics
first workahle baths and began scien- analysis, but important differences can Intermetallics
tific investigations of the process. be found. The most important practical Natural products
This is not a very long history for a differences may include: Fibers
Silicon
technology. Most of the details of its
evolution are still readily available for Deposition rate Particulate Dielechcs
study. These data show that the field F'ractical maximum thickness deposited Glass spheres
has undergone a very rapid initial Stress of deposit Diamonds
expansion in scientific understanding Adhesion to surface Abrasives
Plastics
coupled with a wide range of practical Corrosion resistance
uses. Further technological develop- Crystal structure
ment has continued at a slower pace, Homogeneity of coating thickness
hut usage has been rapidly increasing Ability to coat particular substrates pretreatments needed for plating on
both in terms of number of applications Technical utility such metals as stainless steel, alumi-
and total usage. The field has not yet Reproducibility num, zinc or copper are vastly different
become static or mined out. Cost of deposit but can allow use of one electroless
Looking at the background of the Process hazard formulation on a wide range of sub-
process, it is obvious that electroless Process toxicity strates; for example, aluminum must
plating is not a unique field by itself, Waste products be deoxidized and preferably zincated
but is only one of a series of closely Alloy homogeneity before electroless nickel plating, while
related surface-coating techniques. zinc must be copper-plated i n ~ t e a d . ~ - ~
They can be conveniently divided into Electroless deposition can be con- For nonconductors, room temperature
gas-phase and liquid-phase processes. veniently divided into three general baths are usually used. Nonconductors
The gas-phase types can be easily areas, deposition on metals, on bulk need coating with catalyst to initiate
subdivided into many other categories, dielectrics, and on particulate dielec- plating and usually special etchants ~~~

such as thermal- and electron-beam trics as shown in Table I. These three and other pretreatments are necessary
evaporation, plasma spray or reactive areas in the table mainly correspond to for optimum adhesion and coverage?
sputtering. There are some hasic tech- the basic types of electroless nickel A third area is plating on particulate
nical differences in the way these are baths now available. This is one basis dielectrics.Io This is a much newer
divided. Liquid-phase processes are for commercial product differentiation. field, and baths that are much more
based on reactant reduction by an Intensive research has led not only to stable are needed. Two separate suh-
internal electron flow. Gas-phase proc- special electroless nickel baths for each fields are involved.
esses usually use some form of thermal substrate, but to special pretreatments, One subfield consists of codeposi-
energy input rather than electron flow. which allow the same electroless bath tion of electroless nickel with another
(Some forms of ion plating using a to be used on many substrates. particulate material onto the surface of
charged substrate are exceptions.) In Metals are easily coated with elec- a part. The coating is a two-phase
this view, electroplating and elec- troless deposits using a hot bath. The system that incorporates a continuous

MAY 1992
 ’.,,
electroless nickel phase that acts as a Table II. Electroless Nickel- proven in laboratory use. Most have
binder to hold the particulates. Teflon PhOsDhOrUS Bath TVDeS
.. shown sufficient promise to warrant
deposits obtained via codeposition writing a patent and some are commer-
have superior lubricity and anti-galling Slow or fast rate cially successful now.
Dull or bright
properties.” Aluminum nitride, chro- Low or high phosphorus What does the future hold in store
mium carbidelz and silicon carbide” Regenerable or single use for electroless nickel plating? There is
electroless nickel composites have Hot or room temperature a real need for more fundamental work
very good wear resistance. For grind- Hiah or low stabiiitv on the whole process of electroless
ing wheels, a diamond composite with plating. Much of the available data
electroless nickel yields better proper- were obtained many years ago. Often ~~~

ties for grinding wheel^;^ the addition Commercial interest began around the baths now in use are completely
of 6% graphite reduces the friction and 1950. A vigorous research program different, especially in terms of bath
rate of wear.14 continued for many years at GAT and purity and deposit composition, stabi-
The other subfield consists of coat- at many other labs5 At this time, much lizers and brighteners.
ing only the particles, whether dielec- of the basic science of the process was It is safe to predict that most of the
tric or metallic, to yield discrete parti- understood and most of the commer- new developments will he in the
cles coated with the electroless metal cially important discoveries were application field; however, new pre-
deposit. Glass microballoons coated made. Much work was done on heat treatments will be developed, espe-
with electroless nickel for.laser fusion treatments, corrosion resistance, regen- cially for nonconductors. New alloy
targets, and electroless nickel-coated eration of baths and stabilizers. The combinations will be invented, possi-
diamonds for sintered grinding wheels discovery and development phase bly including leveling electroless nick-
are typical examples. largely ended with the issuance of els or colored coatings. A recent
A wide range of substrates can now GAT patents on plating of particu- development is a method for blacken-
be commercially plated using these l a t e ~and
~ ~with the development of ing an electroless nickel for possible
methods. Although a nickel-phospho- room-temperature baths for plating - on solar applications. Hypophosphite may
IUS alloy is deposited in each case, plastics.’*- face competition by some as-yet-unin-
particular needs have necessitated the The period since the mid-1960s has vented organonitrogen,organophospho-
development of specialized baths. been devoted to consolidation and rus, or organoboron reducing agent.
There are hot baths for metals and refinement of the basic processes and And is it even necessary to mention
some nonconductors, room-tempera- to development of new applications for economics? Cost-cutting processes
ture baths for heat-sensitive materials, electroless-nickelcoatings. Much tech- will be important, but only if they cut
highly stabilized baths for plating on nical information has been developed, total costs. Even then, the customer
fine particles, and even spray solutions especially in the areas of mechanisms, may be unappreciative: for example,
for very rapid deposition on glass for stability, corrosion testing, and E W one customer had a new zinc process
architectural uses. RFI shielding.Ig installed and ran it at a higher current
The other emphasis of product dif- Many specialized applications have density allowing substantially higher
ferentiation focuses not on the sub- been proposed, but not all have been or throughput on his line. The customer
strate but on the bath itself. Table Il will be commercially successful (Table then complained that the process was
shows the types of baths available. The III). All of these ideas have been using up zinc anodes too quickly!
authors estimate that over 200 formula- Environmental regulations will also
tions are available worldwide. Many Table 111. Electroless Nickel influence the future. Users must be-
times that number have been pub- Applications
..
come increasingly conscious of the
lished, exist in the patent literature, or total costs of chemical processing. It is
were simply abandoned.5J5 Magnetic alloys no longer possible to consider only the
The options available are all the Archilectural glass coatings purchase price of solutions. Treatment
more remarkable, because 50 years Improving amalgam adhesion for dental costs, and the effects of the chemicals
fillings
ago, only one basic type of bath (the Consolidation of sand layers durinp oil well on intemal waste stream processing,
“Brenner” bath) was used on mild drilling effluent quality, and final environ-
steel. Coatina” QiaSS
- microsDheres for fusion mental effects must also be considered.
Wurtz’s discovery, around 1845, energy Perhaps. new solutions will be devel-
was that nickel salts and hypo- Initial surface layer on printed circuit boards oped to more safely plate plastics; or
~

Alloys for gold replacement

phosphite react to give a black pow- Diamond plating for grinding wheels perhaps new plastics or plastic-filler
der-a discovery of little use to surface Composite coatings for abrasion resistance combinations will be developed that
finishing.’ Roux and Breteau2J6 dur- Composite coatings with plastics (Teflon)for can be etched without chromic acid.
ing a period around 1915, both found lubricity Permanganate etchants, ozone-
~

Precoat on iron for porcelain coating

that a nickel-phosphorus film could be Brazing alloy on aluminum based etchants, and plasma etching are
formed. Roux received a patent for Coating of stainless steel power for fusibility all in use; for example, in electroless
plating aluminum, but nothing further Coating of plastic and zinc molds nickel, most baths for plating on
was done.2 Brenner independently dis- Replacement of hard chromium plastics contain ammonia. Several
covered the process in 1944 and pur- Use as a nitriding mask states now have very stringent limits
Solar panels
sued and publicized its early develop- EMI/RFI shielding on ammonia discharges, giving rise to
ment for commercial use.’ the development and availability of

26 METAL FINISHING
 new ammonia-free baths, which will troless nickels may be introduced to 4. Krutenat, R.C., “Metallic Coatings,’’ A
start a new learning cycle as they replace the “strike” deposits, or to Concise Encyclopedia of Chemicol Tech-
become more widely used. nology, pp. 749-751; Wiley, New Ymk
function as the sole finish on plastics. 1985
In addition, hot carbonate-buffered This might entail the combined im- 5. Gavrilov, G.G., Chemical (Electroless)
baths are also being developed for provements of better plastics; lower Nickel Plating, Portcullis Press Ltd.,
metal plating. They have a number of temperature, fast-rate, electroless nick- Radhill. Eneland 1979
6. Mallo&, G.yand J. Hajdu (Fds.), Electroless
advantages over the ammonia buffered els; and brighter nickel deposits. Per- Plnting.AESF 1990
baths: they do not fume, so there are no haps electroless nickel deposited on 7. Paunovic, M., and 1. Ohno (Eds.), “Elec-
health or corrosion problems (ammo- superconducting fibers would lead to troless Deposition of Metals and Alloys,”
nia additions must be made frequently new applications. Electroless plating Electrochemical Sociery Proceedings, Val
82-12; 1988
and the inevitable fumes are irritating); from organic solvents is also under 8. Krulik, G.A., “Electroless Plating,” Ency
and carbonate baths bold the proper pH development.15 Electroless coatings clonedia of Chemicol Technolorv. 3rd Ed..
range much better because the compo- are being used increasingly for EMU pp:738-7+0, Wiley, New York”i979
nents are not volatile (additions are RFI shielding and for electrostatic 9. Krulik, G.A., “Electroless Plating of Plas-
infrequent and consist of liquid caustic tics,” Journal of Chemicol Education,
discharge elimination. Processing labo- 55(6):361-365: 1978
01 carbonate solutions). ratories may disclose completely new 10. Henry, J., “Electroless (Autocatalytic,
In m e cases, bum-off is less with applications or may show that some Chemical) Plating,” Met01 Finishing,
the carbonate bath. Deposition rates properties are greatly enhanced when 90(1A):353-366: 1991
plating is done in a microgravity field. 11. lhlsi, S.S., “Electroless Nickel: PTFE
arc similar to ammonia baths, so no Composite Coatings.” Transactions of the
he-cycle changes are needed. The New alloys will be developed for Institute ofMetal Finishing 61(4):147: 1983
same racks, rack coatings, and tanks special uses, and still other applica- 12. Dennis, J.K.,et al., “Electroless Composite
may be used. Waste treatment is much tions may be developed to take advan- Coating,” Tramactions of the Imtituie of
tage of the amorphous structure of Metal Finishing, 59(4): 118; 198 1
simpler, since no ammonia is present 13. Hubbell, F.N., ”Chemically Deposited
to redissolve precipitated metals or electroless deposits to help solve inter- Composites,” Ploting and Surjkface Finish-
violate effluent limits. Also, plating granular corrosion problems. ing, 65(12):58; 1978
du”m with carbonate-buffered 14. Izzard, M., and I. K. Dennis, “Deposition
baths results in better adhesion and and Properlies of Electroless NickelIGraph-
CONCLUSION ite Coatings,” Transactions of the Institute
reduced blistering. ofMetal Finishing 65(3):85; 1987
There are a few cautions to observe The fifty-year-old electroless nickel- 15. Domino, EA., (Ed.) Plating of Plastics:
with the carbonate-based plating on plating field is far from being static. Recent Developments, Noyes Data Corp.,
Park Ridge, N.J.; 1979
plastic baths. The most dramatic is that New discoveries and applications will 16. Duffy, J.F., (Ed.) Electroless and Other
the. bath color is green, not blue. This continue to expand the frontiers of Non- Electrolvtic Plotinn Technioue.7: Re-
will actually help operators realize that electroless plating. MF cent Developments, Noyes Data Corp., Park
the bath is now different and should be Ridge, N.I.; 1980
treated differently. Good water quality References 17. Parker,K.,U.S.Patent3,562,000, 1971
18. Muller, G., and D. Baudrand, Platrng ABS
is essential for bath makeup, and I. BreMer. A,. “A History of the Electroless Plastics. Robert Draper Ltd.. Molesev, Sur-
preferable for the rinse before plating. Plating Process,” Symposium on Elec- rey. England; 1967
troless Nickel Plating, ASTM Special Tech- 19. Krulik, G.A., “Corrosion Resistance of
Continuous 10-25 micron filtration is nical Publication No. 265; 1959
mommended during plating. Electroless Deposits for Electromagnetic
2. ROUX,F.A..U.S. Patent 1,207,218; 1916 Interference Shielding,” Plating and Sur-
In other applications, faster elec- 3. Wurtz, A,, Comptes Rendw, 21:149; 1845 face Finishing, 12565% 1984

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