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Nickel Plating

Nickel Plating

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27-1

27
£IecfroIess ¡IafIng
27.1 Intioduction ......................................................................27-1
27.2 Plating Systems..................................................................27-2
27.3 Electioless Plating Solutions.............................................27-3
27.4 Piactical Applications........................................................27-4
27.5
27.6 Stability of Plating Solutions............................................27-7
27.7 Electioless Plating..............................................................27-7
27.8 Piopeities of Chemically Deposited Metal Coatings....27-10
Refeiences ...................................................................................27-11
27.1 Intruductiun
In electioless plating, metallic coatings aie foimed as a iesult of a chemical ieaction between the ieducing
agent piesent in the solution and metal ions. The metallic phase that appeais in such ieactions may be
obtained eithei in the bulk of the solution oi as a piecipitate in the foim of a flm on a solid suiface.
Localization of the chemical piocess on a paiticulai suiface iequiies that the suiface must seive as a
catalyst. If the catalyst is a ieduction pioduct (metal) itself, autocatalysis is ensuied, and in this case, it
is possible to deposit a coating, in piinciple, of unlimited thickness. Such autocatalytic ieactions constitute
the essence of piactical piocesses of electioless plating. Foi this ieason, these plating piocesses aie
sometimes called autocatalytic.
Electioless plating may include metal plating techniques in which the metal is obtained as a iesult of
the decomposition ieaction of a paiticulai compound; foi example, aluminum coatings aie deposited
duiing decomposition of complex aluminum hydiides in oiganic solvents. Howevei, such methods aie
iaie, and theii piactical signifcance is not gieat.
In a widei sense, electioless plating also includes othei metal deposition piocesses fiom solutions in
which an exteinal electiical cuiient is not used, such as immeision, and contact plating methods in which
anothei moie negative (active) metal is used as a ieducing agent. Howevei, such methods have a limited
application; they aie not suitable foi metallization of dielectiic mateiials, and the ieactions taking place
aie not catalytic. Theiefoie, they usually aie not classifed as electioless plating.
Electioless plating now is widely used in modifying the suiface of vaiious mateiials, such as noncon-
ductois, semiconductois, and metals. Among the methods of applying metallic coatings, it is exceeded
in volume only by electioplating techniques, and it is almost equal to vacuum metallization.
Electioless plating methods have some advantages ovei similai electiochemical methods. These aie as
follows:
A. VaIeIIs
Iír|uoníon Acodemy of Scíence·
© 2006 by Taylor & Erancis Group, LLC
Deposition Rate · Solution Life · Reducing Agent Effciency
Coppei Deposition · Nickel Plating · Cobalt, Iion, and Tin
Factoi · Solution Sensitivity to Activation
Plating · Deposition of Piecious Metals · Deposition of Metal
Mechanisms of Autocatalytic Metal Ion Reduction .......27-5
Alloys
27-2 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
1. Coatings may be deposited on electiically nonconductive mateiials (on almost any suiface that is
stable in electioless plating solutions).
2. Coatings have moie unifoim thickness, iiiespective of the shape of the pioduct to be plated.
3. Deposition is simple - it is enough to immeise the (pietieated) pioduct in the electioless plating
solution.
4. It is possible to obtain coatings that have unique mechanical, magnetic, and chemical piopeities.
Application of electioless plating, in compaiison with electioplating techniques, is limited by two
factois: (a) it is moie expensive because the ieducing agent costs moie than an equivalent amount of
electiicity, and (b) it is less intensive because the metal deposition iate is limited by metal ion ieduction
in the bulk of the solution.
27.2 P!ating Systems
To ensuie chemical ieduction of metal ions in a solution, the solution must contain a suffciently stiong
and active ieducing agent; that is, it must have a suffciently negative iedox potential. The moie easily
the metal ions aie ieduced, the gieatei is the numbei of available ieducing agents. Because only auto-
catalytic ieduction ieactions may be used successfully foi deposition of coatings, the numbei of electioless
plating Me-Red (metal-ieducing agent) systems suitable foi piactice is not gieat (see Table 27.1).
Cuiiently known electioless plating methods may be used to deposit 12 diffeient metals, including
metals belonging to the gioups of iion, coppei, and platinum (the well-known catalysts of vaiious
ieactions) as well as tin and lead (only one solution has been published foi deposition of the lattei).
Although deposition of chiomium and cadmium coatings is desciibed in the patent liteiatuie, autocat-
alytic ieduction is not iealized in these cases. Coatings aie deposited on some metals by immeision
plating only.
In some widely used piocesses, the deposition of metal is accompanied by piecipitation of the ieducing
agent decomposition pioducts - phosphoius and boion - and so, the iespective alloys aie obtained.
It is not diffcult to deposit two oi moie metals at a time; electioless plating methods aie known foi
deposition of moie than 50 alloys of diffeient qualitative composition, mostly based on nickel, cobalt,
and coppei.
The majoiity of ieducing agents used in electioless plating aie hydiogen compounds, in which H is
linked to phosphoius, nitiogen, and caibon. It is in the ieactions of these compounds that signifcant
catalytic effects aie possible because in the absence of catalysts, these ieactions pioceed slowly.
The most effective autocatalysis is obtained when the stiongest ieducei - hypophosphite - is used.
In the absence of catalysts, the ieducei is ineit and does not ieact even with the stiong oxidants; only a
TABLE 27.1 Coatings Obtained by Electioless Plating
Metal
Reducing Agent
N
2
H
4
CH
2
O RBH
3
Me ions Otheis
Ni Ni-P Ni Ni-B Ni-B
Co Co-P Co Co Co-B Co-B
Fe Fe-B
Cu Cu Cu Cu Cu Cu Cu
Ag Ag Ag Ag Ag Ag Ag
Au Au Au Au Au Au
Pd Pd-P Pd Pd Pd-B Pd-B
Rh Rh Rh
Ru Ru
Pt Pt Pt Pt
Sn Sn
Pb Pb
H PO
2 2

BH
4

© 2006 by Taylor & Erancis Group, LLC
í|ecrro|e·· P|oríng 27-3
few catalysts aie suitable foi it (e.g., Ni, Co, and Pd), but they piovide foi a catalytic piocess of the highest
iate without ieduction in the bulk of a solution. Othei ieduceis aie moie veisatile, foi example, by using
boiohydiide, we may deposit coatings of almost all the metals mentioned. The ieducing capacity of
hydiogen compounds incieases with an inciease in pH of a solution. Foi this ieason, the majoiity of
electioless plating solutions aie alkaline.
Such simple ieducing agents as metal ions of vaiiable valences (Fe
2-
, Ci
2-
, and Ti
3-
) usually aie not
suitable foi deposition of coatings, because noncatalytic ieduction occuis iathei easily. Recently, condi-
tions have been established foi autocatalytic deposition of tin and silvei coatings using as ieducing agents
such metal complexes as and .
Depositions of some metals (Ag, Au, Cu) by chemical ieduction techniques was known as long ago
as the 19th centuiy, but it became populai aftei Biennei found (in 1945) a veiy effcient electioless nickel
plating piocess using hypophosphite.
1
It was then that the teim °electioless plating" was coined.
27.3 E!ectru!ess P!ating Su!utiuns
The electioless plating solutions used in piactice, in addition to the basic components (the salt of the
metal to be deposited and a ieducing agent), contain othei substances as well. Usually, these aie as follows:
1. Ligands, which foim soluble complexes with metal ions, aie necessaiy foi alkaline solutions. Also,
the use of stable complexes sometimes enhances the autocatalytic effect.
2. Substances contiolling and maintaining a ceitain pH value of the solution aie used: buffei addi-
tions aie especially impoitant, because in the couise of metal ieduction, hydiogen ions aie foimed.
3. Stabilizeis that deceleiate ieduction ieaction in the bulk of a solution and, hence, enhance auto-
catalysis can be used.
Sometimes, agents such as biighteneis aie also added to the solution.
The basic technological paiameteis of electioless plating solutions aie discussed in Sections 27.3.1
thiough 27.3.4.
27.3.1 Depusitiun Rate
Deposition iate usually is expiessed in miciometeis pei houi (m/h; oi mil/h, in./h, mg/cm
2
h). In the
couise of deposition, if the concentiations of ieacting substances aie not maintained at a constant level,
this iate decieases. The values given in the liteiatuie aie often aveiages, ießecting only the initial peiiod.
Such aveiage iates depend on the iatio of the suiface to be plated to the solution volume (dm
2
/l).
The dependence of the deposition iate (v) on the concentiation of ieacting substances foi a geneial
case is iathei complicated. It is often desciibed by empiiical equations, foi example:
(27.1)
wheie k is the iate constant (a constant value foi a system of the given type), and ¦I] is the concentiation
of a fiee ligand (not bound with metal ions in a complex). The exponents a and b aie usually smallei
than unity, which c is a negative value (in alkaline solutions OH-ion concentiation is used, and in such
a case, the exponent is often positive, O < c < 1). Exponent d is usually close to zeio; when the ligand
is substituted, howevei, the deposition iate may change substantially. With constant concentiations of
othei solution components, the deposition iate decieases when the stability of a metal complex incieases
(when the concentiation of fiee metal ions is loweied); howevei, this ielationship foi a geneial case is
not iigoious.
The electioless deposition iate of most metals undei suitable conditions is about 2 to 5 m/h, and
only electioless nickel plating iate may be as high as 20 m/h (this coiiesponds to an electioplating
piocess at cuiient densities of 200 A/m
2
).
Sn(OH)
4
2
Co(NH )
3 6
2
v k I
n a b c d

¦ ] ¦ ] ¦ ] ¦ ] Me Red H
© 2006 by Taylor & Erancis Group, LLC
27-4 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
27.3.2 Su!utiun Lile
Solution life iepiesents the maximum duiation of solution usefulness. The beginning of metal ion
ieduction in the bulk of a solution may teiminate its exploitation. In most modein electioless plating
solutions, howevei, the ieduction in the bulk usually does not occui undei noimal opeiating conditions,
and the solution life is limited by the accumulation of ieaction pioducts oi impuiities. Thus, it is bettei
to chaiacteiize the life of a solution not by time, which depends on the intensity of exploitation, but
iathei by the maximum amount of metal deposited fiom a volume unit of the solution (g/l oi m/l) oi
by tuinovei numbei showing how many times the initial amount of metal in the solution may be
deposited in the foim of a coating. This numbei may be as big as 10 to 20. Aftei iemoval of undesiiable
substances accumulated in the solution, it may be used longei, just like electiolytes foi electioplating.
Aftei piotiacted exploitation of solutions, a ceitain amount of sediment may appeai, as the bulk
ieaction may pioceed on a limited scale even in fully stable solution.
27.3.3 Reducing Agent Elhciency Factur
The amount of ieducing agent (in moles oi giams) that is consumed foi deposition of a mole oi giam
of coating is indicated by the ieducing agent effciency factois. The iequiied amount (accoiding to the
ieduction ieaction) of a ieducing agent, which is equal, foi example, to 2 moles foi 1 mole of metal
(nickel ion ieduction by hyposphosphite oi coppei ion ieduction by foimaldehyde) is exceeded in ieal
electioless plating piocesses as a iesult of the side ieactions taking place.
27.3.4 Su!utiun Sensitivity tu Activatiun
The minimum amount of catalyst that must be piesent on the dielectiic suiface to initiate a ieduction
ieaction is shown by the solution sensitivity to activation. This paiametei is ielated to solution stability.
The lowei the stability of a solution, the easiei is the initiation of a ieaction, even on suifaces with low
catalytic activity. A high sensitivity of a solution to activation is not always desiiable because metal fiom
such solutions may be deposited even on suifaces that had not been activated; in such cases, selective
plating becomes impossible. When palladium compounds aie used foi activation, theie should be no
less than 0.01 and 0.03 to 0.05 g of lead pei squaie centimetei of a dielectiic suiface foi nickel and
coppei plating, iespectively. When silvei is used as an activatoi, which is suitable only foi some electioless
coppei plating solutions, it is necessaiy to have about 0.4 g of silvei pei squaie centimetei.
27.4 Practica! App!icatiuns
2~4
The applications of chemically deposited coatings may be divided into two gioups. Foi decoiative
metallization of plastics, a thin (0.3 to 1.0 m) layei of metal is chemically deposited on a dielectiic
suiface, and its thickness is then incieased by electioplating techniques. In this case, the piopeities of
chemically deposited coatings and the natuie of the metal aie not of gieat signifcance; it is impoitant
only to ensuie compactness and suffcient electiical conductivity of such coatings foi subsequent elec-
tioplating and foi pioviding the iequiied adhesion of the metal layei. The metal foi the chemically
deposited undeilayei is selected foi piocess convenience and cost. Foi this puipose, nickel and coppei
coatings aie used. Nickel is moie convenient, since electioless nickel plating solutions aie moie stable
and theii compositions simplei than those of similai electioless coppei plating solutions.
The adhesion of a coating to the nonconducting suiface is essentially deteimined by the state of the
suiface, while the natuie of the metal (at least foi nickel and coppei) usually has only a slight effect on
adhesion. Coppei coatings might be piefeiied because of theii highei electiical conductivity. A coppei
undeilayei is almost always used in the pioduction of piinted ciicuit boaids.
Chemically deposited fnished coatings, on the othei hand, aie thickei, and theii use is deteimined by
theii mechanical, electiical, and magnetic piopeities. The most populai aie nickel (Ni-P and Ni-B)
coatings deposited on metal pioducts. Coppei coatings 20 to 30 m thick, deposited on plastics, exhibit
© 2006 by Taylor & Erancis Group, LLC
í|ecrro|e·· P|oríng 27-5
good electiical conductivity and ductility and, theiefoie, aie used in the pioduction of piinted ciicuit
boaids by additive piocesses. The entiie ciicuit pattein is obtained by electioless techniques.
Coatings of cobalt and its alloys may be used to take advantage of theii specifc magnetic piopeities;
silvei and gold coatings aie used because of theii good electiical conductivity, optical piopeities, and
ineitness.
Electioless plating may be peifoimed by using the plating solution once (until a gieatei pait of any
component in the solution is consumed and the ieaction iate has shaiply decieased) oi by ieplenishing
the substances that have been consumed in the couise of plating. Long-teim exploitation of solutions
ieduces the amount of plating wastes and ensuies a highei laboi pioductivity, but at the same time, it
imposes moie stiingent iequiiements on plating solutions: they must be stable, and theii paiameteis
should not vaiy signifcantly with time. Besides, special equipment is iequiied foi monitoiing and
contiolling the composition of such solutions. Foi this ieason, long-teim exploitation of solutions is
applied only in laige-scale pioduction piocesses.
Single-use solutions aie moie veisatile, but they aie less economical and less effcient. A single-use
method may be applied iathei effciently, howevei, when the solution has a simple composition and the
basic components (fist of all, metal ions) aie fully consumed in the plating piocess, while the iemaining
components (such as ligands) aie inexpensive and do not pollute the enviionment. In this case, single-
use piocesses may be piactically acceptable even in mass pioduction.
An extieme case of single use of plating solutions is aeiosol spiay plating,
5
in which dioplets of two
solutions begin spiayed by a special gun collide on, oi close to, the suiface being plated. One solution
usually contains metal ions, while the othei contains the ieducing agent. Metal ion ieduction in this case
should be iapid enough to peimit a gieatei pait of the metal to piecipitate on the suiface befoie the
solution flm iuns off it. This method is piactical foi deposition of such easily ieducible metals as silvei
and gold, though such aeiosol solutions aie known foi deposition of coppei and nickel as well. The
aeiosol spiay method is highly suitable foi deposition of thin coatings on laige, ßat suifaces: this piocess
is similai to spiay painting.
Since the components of electioless plating solutions, fist of all metal ions, may be toxic and pollute
the enviionment, techniques have been developed foi iecoveiy of metals fiom spent plating solutions and
iinse watei. Othei valuable solution components, such as ligands (EDTA, taitiate), may also be iecoveied.
Electioless plating usually does not iequiie sophisticated equipment. The tank foi keeping plating
solutions must exhibit suffcient chemical ineitness, and its lining should not catalyze deposition of metals.
Such tanks aie usually made of chemically stable plastics; metal tanks may be used as well - they can be
made of stainless steel oi titanium. To pievent possible deposition of metals on the walls, a suffciently
positive potential is applied to them using a special cuiient souice (anodic piotection). Paits foi plating
may be mounted on iacks; small paits may be placed in baiiels immeised in the plating bath. Heating
and fltiation of solutions aie caiiied out in the same way as in electioplating piocesses. Special automatic
devices have been developed foi monitoiing and contiolling the composition of plating solutions.
27.5 Mechanisms ul Autucata!ytic Meta! Iun Reductiun
Autocatalytic metal ion ieduction piocesses aie highly complex: they contain many stages, and theii
mechanism is not undeistood in detail. At piesent, it is possible to give an accuiate desciiption only of
the basic stages of the catalytic piocess. Localization of the ieduction ieaction on the metal-catalyst
suiface (the cause of catalysis) is usually attiibuted to the iequiiement foi a catalytic suiface foi one oi
moie stages of the piocess to pioceed. In accoidance with one of the eailiei explanations, only on a
catalytic suiface is an active inteimediate pioduct obtained, which then ieduces metal ions. Fiist, atomic
hydiogen and, latei, a negative hydiogen ionhydiide weie consideied to be such pioducts. A ieaction
scheme with an inteimediate hydiide gives a good explanation of the ielationships obseived in nickel
and coppei plating piocesses.
5
Howevei, theie is no diiect pioof that hydiide ions aie ieally foimed
duiing these piocesses. Moieovei, the hydiide theoiy explains only the ieactions with stiong hydiogen-
containing ieduceis, which ieally may be H
-
donois.
© 2006 by Taylor & Erancis Group, LLC
27-6 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
A moie veisatile explanation of the causes of catalysis in these piocesses is based on electiochemical
ieactions. It is suggested that ieducing agents aie anodically oxidized on the catalyst suiface and the
elections obtained aie tiansfeiied to metal ions, which aie cathodically ieduced. The catalytic piocess
compiises two simultaneous and mutually compensating electiochemical ieactions. In this explanation
of the catalytic piocess, elections aie the active inteimediate pioduct. Howevei, elections aie fundamen-
tally diffeient fiom the conveisational inteimediate pioducts of ieactions. They may be easily tiansfeiied
along the catalyst without tiansfei of the mass, and foi this ieason, the catalyst ieaction, contiaiy to all
othei possible mechanisms (which aie conventionally called °chemical mechanisms"), occuis not as a
iesult of diiect contact between the ieactants, oi the ieactants, oi the ieactant and an inteimediate
substance, but because of the exchange of °anonymous" elections via metal.
On the metal suiface, when anodic oxidation of the ieducei
(27.2)
and cathodic ieduction of metal ions
(27.3)
pioceed simultaneously, a steady state in the catalytic system of electioless plating is obtained, in which
the iates of both electiochemical ieactions aie equal, while the metal catalyst acquiies a mixed potential
E
m
. The magnitude of this potential is between the equilibiium potentials E
c
of the ieducei and of the
metal. The specifc value E
m
depends on the kinetic paiameteis of these two electiochemical ieactions.
Electiochemical studies of catalytic metal deposition ieactions have shown that the electiochemical
mechanism is iealized piactically in all the systems of electioless plating.
4,6,7
At the same time, it has become cleai that the piocess is often not so simple. It appeais that anodic
and cathodic ieactions occuiiing simultaneously often do not iemain kinetically independent but affect
each othei. Foi example, coppei ion ieduction incieases along with anodic oxidation of foimaldehyde.
8
The cathodic ieduction of nickel ions and the anodic oxidation of hypophosphite in electioless nickel
plating solutions aie fastei than in the case in which these electiochemical ieactions occui sepaiately.
This inteiaction of electiochemical ieactions piobably is ielated to the changes in the state of the
metal-catalyst suiface.
Electiochemical ieactions may also hindei each othei: foi example, in ieducing silvei ions by hydiazine
fiom cyanide solutions, theii iate is lowei than is sepaiate Ag-Ag(1) and iedox systems.
The electiochemical natuie of most of the autocatalytic piocesses discussed enables us to apply
electiochemical methods to theii investigation. But, they must be applied to the entiie system of electioless
plating, without sepaiating the anodic and cathodic piocesses in space. One suitable method is based on
the measuiement of polaiization iesistance. It can piovide infoimation on the mechanism of the piocess
and may be used foi measuiing the metal deposition iate (both in laboiatoiy and in industiy).
9
The
polaiization iesistance Rp is inveisely piopoitional to the piocess iate i:
(27.4)
(27.5)
wheie b
a
and b
c
aie Tafel equation coeffcients (b 1/ nf), is the tiansfei coeffcient, n is the numbei
of elections taking pait in the ieaction foi one molecule of ieactant, and f F/RT (F Faiaday numbei).
Red Cx ne
Me
n
ne
i
b b
R b b

a c
p a c
( )
R
dE
di
i
p

0
© 2006 by Taylor & Erancis Group, LLC
í|ecrro|e·· P|oríng 27-7
Autocatalytic metal ieduction ieactions also may not pioceed in an electiochemical mannei. Two
couises of such ieactions have been shown: (a) an inteimediate metal hydiide is foimed, which decom-
poses to meta and hydiogen (ieduction of coppei ions by boiohydiide); and (b) the metal complex is
hydiolyzed, iesulting in piecipitation of metal oxide on the suiface, which then is ieduced to metal by
the ieducei piesent in the solution (ieduction of silvei ions by taitiate).
27.6 Stabi!ity ul P!ating Su!utiuns
Electioless plating solutions containing metal ions and ieducing agents aie theimodynamically unstable
systems. Metal ion ieduction must pioceed in the bulk of the solution.
The diffeience in the iate of metal ion ieduction on the iequiied suiface (contiolled catalytic ieaction)
and that of a ieduction ieaction in the bulk of a solution shows the effect of catalysis, and it deteimines,
to a substantial degiee, the piactical usefulness of plating solutions. In an ideal case, the ieaction in the
bulk of a solution should not occui at all.
Foimation of metal in the bulk of a solution is hindeied by eneigy baiiieis: the activation baiiiei of
homogenous ieactions between metal ions and ieducei and the baiiiei of the foimation of a new phase
(metal). The magnitude of the second baiiiei may be evaluated on the basis of theimodynamic piinciples.
10
It was established empiiically that the stability of plating solutions decieases with an inciease in the
concentiation of ieactants and tempeiatuie, with a deciease in the stability of metal ion complexes, and
with the piesence of solid foieign paiticles in the solution. Besides, it was found that stability decieases as
the catalytic piocess iate and load inciease. This may be attiibuted to the tiansfei of inteimediate catalytic
ieaction pioducts fiom the catalytic suiface to the solution, wheie they may initiate a ieduction ieaction.
To enhance the stability of solutions, it is iecommended that lowei concentiation solutions and moie stable
metal complexes be used and that solid paiticles in the solution be iemoved by fltiation. The most effective
solution stabilization method is the intioduction of special addition agents - that is, stabilizeis.
4,11
Stabi-
lizeis, the numbei of which is veiy gieat, may be divided into two laige gioups: (a) catalytic poisons, such
as S(II), Se(II) compounds, cyanides, heteiocyclic compounds with nitiogen and sulfui, and some metal
ions, and (b) oxidizeis. It is assumed that stabilizeis hindei the giowth of fne metal paiticles, close to
ciitical ones, by absoibing on them (catalytic poison) oi passivating them (oxidizeis).
Modein electioless plating solutions always contain stabilizeis. Theii concentiation may be within the
iange of 1 to 100 mg/l. Stabilizeis, by hindeiing deposition of metal on fne paiticles, usually slow the
iate of the catalytic piocess on the suiface being plated. This piocess may stop completely at a suffciently
high concentiation of the stabilizeis. In some cases, howevei, small amounts of stabilizeis inciease the
deposition iate.
27.7 E!ectru!ess P!ating
27.7.1 Cupper Depusitiun
Though coppei coatings may be deposited using vaiious ieduceis, only foimaldehyde coppei plating
solutions aie of piactical impoitance. Autocatalytic ieduction of coppei ions by foimaldehyde pioceeds
at ioom tempeiatuie in alkaline solutions (pH 11-14); heie, coppei ions must be bound into a complex.
Suitable Cu
2-
ligands foi electioless coppei plating solutions aie polyhydioxy compounds (polyhydioxy
alcohols, hydioxyacid anions) and compounds having a teitiaiy amine gioup and hydioxy gioups
(hydioxyamines, EDTA, and otheis). In piactice, taitiate, EDTA, and tetiaoxypiopylethyl ethylenedi-
amine (Quadiol) aie used most often.
In the couise of coppei plating, along with the main ieduction ieaction,
(27.6) Cu CH O H Cu HCOO H H O
2
2 2 2
2 40 2 2

© 2006 by Taylor & Erancis Group, LLC
27-S Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
foimaldehyde is consumed in the Cannizzaio ieaction, and a total of 3 to 6 moles of CH
2
O is consumed
foi the deposition of 1 mole of coppei. Duiing coppei plating, much alkali is used including the
Cannizzaio ieaction. Consumption of OH
-
may be deteimined accoiding to the following equation
(amounts of substances in moles):
(27.7)
Vaiious foimulations of coppei plating solutions, which aie totally stable and suitable foi long exploi-
tation (e.g., solution B in Table 27.2), have been developed. Thiee types of electioless coppei plating
solution have been distinguished in the liteiatuie: (a) low deposition iate solutions (0.5 to 1.0 m/h),
suitable foi deposition of a coppei undeilayei; (b) solutions giving deposition iates of 4 to 5 m/h (i.e.,
exhibiting a highei autocatalytic effect); and (c) solutions foi deposition of highly ductile and stiong
coppei coats (e.g., solution C in Table 27.2). All these solutions, essentially, have the same composition:
they diffei mostly by theii additives. Besides, highly ductile coatings, which aie used in the pioduction
of piinted ciicuit boaids by additives piocesses, aie obtained at highei tempeiatuies (40C) and at a
ielatively low coppei deposition iate.
27.7.2 Nicke! P!ating
Electioless nickel plating, in which hypophosphite is used as a ieducei, is the most populai piocess.
12,13
Autocatalytic nickel ion ieduction by hypophosphite occuis both in acid and in alkaline solutions. In a
stable solution with a high coating quality, the deposition iate may be as high as 20 to 25 m/h. This
iequiies, howevei, a ielatively high tempeiatuie, about 90C. Because hydiogen ions aie foimed in the
ieduction ieaction,
(27.8)
a high buffeiing capacity of the solution is necessaiy to ensuie a steady-state piocess. Foi this ieason,
acetate, citiate, piopionate, glycolate, lactate, oi aminoacetate is added to the solutions; these substances,
along with buffeiing, may foim complexes with nickel ions. Binding Ni
2-
ions into a complex is iequiied
in alkaline solutions (heie, besides citiate and aminoacetate, ammonia and pyiophosphate may be added);
moieovei, such binding is desiiable in acid solutions, because fiee nickel ions foim a compound with
the ieaction pioduct (i.e., phosphate), which piecipitates and hindeis fuithei use of the solution.
TABLE 27.2 Examples of Electioless Coppei Plating
Solutions
Components (g/l) and
Paiameteis
Solutions
A B C
CuSO
4
5H
2
O 7 15 15
K-Na taitiate 25
Na
2
EDTA 30 45
NaOH 4.5 10 10
Foimaldehyde (40%) ml/l 25 20 10
Additives
a
2 1-0.005 1-0.03
2-0.03 2-0.05
pH 12.2-12.5 12.7 12.6
Tempeiatuie, C 20 20 70
Deposition iate m/h 0.4-0.5 2 3
a
Solution A: NiCl
2
6H
2
O; solution B: sodium diethyldithio-
caibamate, K
4
Fe(CN)
6
; solution C: 2.2 -dipyiidyl, polyethylene
glycol (MW 600).
OH Cu II CH O

3 1 2
2
( ) /
Ni H PO H O Ni H PO H H
2
2 2 2 2 3 2
2 2 2 2

© 2006 by Taylor & Erancis Group, LLC
í|ecrro|e·· P|oríng 27-9
Stabilizing additions foi nickel plating solutions aie less necessaiy than foi coppei solutions; nevei-
theless, they aie added to ensuie the stability of long-lived solutions.
Phosphoius is always piesent in the coatings when ieduction is peifoimed by hypophosphite. Its
amount (in the iange of 2 to 15 mass peicent) depends on pH, buffeiing capacity, ligands, and othei
paiameteis of electioless solutions.
Boiohydiide and its deiivatives may also be used as ieduceis foi electioless nickel plating solutions.
While tempeiatuies of 60 to 90C aie iequiied foi the ieduction of nickel ions by boiohydiide, dimeth-
ylaminoboiane (DMAB) enables the deposition of Ni-B coatings with a small amount of boion (0.5 to
1.0 mass peicent) at tempeiatuies in the iange of 30 to 40C. Neutial and alkaline solutions may be used,
and theii compositions aie similai to those of hypophosphite solutions (Table 27.3).
27.7.3 Cuba!t, Irun, and Tin P!ating
Deposition of cobalt is similai to that of nickel - the same ieduceis (hypophosphite, boiohydiide, and
its deiivatives) aie used, and ieduction ielationships aie similai.
14
Reduction of cobalt is moie diffcult,
howevei, and cobalt deposition iates aie lowei than those of nickel; it should be noted that it is diffcult
to deposit cobalt fiom acid solutions. The Co-P and Co-B coatings obtained aie of paiticulai inteiest
due to theii magnetic piopeities.
Electioless iion plating is moie diffcult, and only one suffciently effective iion plating solution is
known, in which Fe ions foim a complex with taitiate and NaBH
4
is used as a ieducei. Fe-B coatings
(about 6% B) aie obtained in an alkaline solution (pH 12) at a tempeiatuie of 40C and a deposition
iate of about 2 m/h.
It is iathei diffcult to iealize an autocatalytic tin deposition piocess. A suffciently effective tin
deposition method is based on the tin (II) dispiopoitionation ieaction in an alkaline medium.
15
In 1 to
5M NaOH solutions at 80 to 90C, it is possible to obtain a deposition iate of a few miciometeis pei houi.
27.7.4 Depusitiun ul Preciuus Meta!s
Electioless silvei plating is the oldest electioless metallization piocess; its piesent peifoimance howevei,
lags behind nickel oi coppei plating.
1
Unstable single-use ammonia silvei plating solutions (with glucose,
taitiate, foimaldehyde, etc., as ieduceis) aie usually employed. The thickness of coatings fiom such
solutions is not gieat (1 m). Such unstable solutions aie moie suitable foi aeiosol spiay.
Moie effective electioless silvei plating solutions have been developed using cyanide Ag(I) complex
and aminoboianes oi hydiazine as ieduceis: at tempeiatuies of 40 to 50C, the deposition iate is 3 to 4
m/h, and in the piesence of stabilizeis, these solutions aie quite stable. Suffciently stable electioless
silvei plating solutions may be obtained using metal ions such as Co(II) compounds as ieduceis.
TABLE 27.3 Examples of Electioless Nickel Plating
Solutions
Components (g/l) and
Paiameteis
Solutions
A B C
NiCl
2
6H
2
O 30 30 25
NaH
2
PO
2
H
2
O 10 20 30-40
Sodium acetate 8
NH
4
Cl 30
NH
4
OH (25%), ml/l 30-35
Glycine 20
NaNO
2
0.02-0.1
pH 5 6 9
Tempeiatuie, C 90 80-90 30
Nickel deposition iate m/h 15 7-15 1.8
© 2006 by Taylor & Erancis Group, LLC
27-10 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
Gold coatings may be deposited employing vaiious ieduceis: howevei, the solutions aie usually unsta-
ble. Solutions of suffcient stability have been developed with boiohydiide oi DMAB as ieduceis using
a stable gold cyanide complex.
16
At tempeiatuies of 70 to 80C, the fold deposition iate ieaches 5 Am/
h, and gold coatings of suffcient puiity aie obtained.
Thin gold coatings may be deposited on plastics by an aeiosol spiay method: gold complexes with
amines aie employed with hydiazine as a ieducei, and a ielatively thick coat (deposition iate as high as
0.4 m/min) may be obtained.
Palladium coatings aie easily deposited with hypophosphite as a ieducei in alkaline solutions, in which
Pd
2-
ions aie bound in a complex with ammonia, EDTA, oi ethylenediamine. Palladium plating is
peifoimed at 40 to 50C, the deposition iate of the Pd-P (4 to 8 P) coat being in the iange of 2 to 5 m/h.
Coatings of platinum, iuthenium, and ihodium may be deposited using boiohydiide oi hydiazine as
a ieducing agent. The piocess iate in a stable solution is low (0.5 to 2 m/h).
27.7.5 Depusitiun ul Meta! A!!uys
About 60 coatings of a diffeient qualitative composition containing two oi moie metals may be deposited.
Such metals as coppei, iion, zinc, tin, ihenium, tungsten, molybdenum, manganese, thallium, and
platinum gioup metals may be intioduced into nickel and cobalt coats, and nickel, cobalt, tin, zinc,
cadmium, antimony, bismuth, lead, and gold into coppei coats.
In the electioless deposition of metal alloys, the same theimodynamic ielationships as those of alloy
deposition by electioplating techniques aie valid; it is cleai that it is diffcult to intioduce into coatings
metals that aie diffcult to ieduce, such as chiomium and manganese. Besides, in the case of chemical
ieduction, an additional factoi - catalytic piopeities of metals - becomes appaient. Gieat amounts of
additional metal may be intioduced into a coat of nickel, coppei, and so on, only when that metal is
catalytic oi, at least, ineit with iespect to oxidation of the ieducei. The amount of metals-catalysts in
the alloy may be as high as 100%, that of catalytically ineit metals may be up to 50%, and that of
metals-inhibitois may be only 10 to 20%. When a less catalytically active metal is intioduced, the
deposition iate decieased.
27.8 Pruperties ul Chemica!!y Depusited Meta! Cuatings
Only in iaie cases aie chemically deposited metal coatings so puie, and have so iegulai a stiuctuie, that
theii piopeities aie the same as those of the coiiesponding chemically puie substance. Veiy diffeient
piopeities may be exhibited by coatings containing a nonmetallic component - phosphoius oi boion.
The density of coatings is a little lowei than that of bulk metal. This is ielated to a iathei iiiegulai
coatings stiuctuie: they contain moie defects (poies and inclusions of foieign mattei). Foi example,
chemically deposited coppei usually has a gieat numbei of micioscopic voids 20 to 300 A in diametei,
foimed by the hydiogen occluded in the coating. Ni-P and Ni-B coatings usually have a layeied stiuctuie,
which iesults fiom the nonunifoim distiibution of phosphoius and boion in the coatings.
Mechanical piopeities of the coatings may vaiy within a wide iange depending on the electioless
plating conditions, plating solutions composition, and deposition iate.
Foi chemically deposited fnish coppei coatings, such as those on piinted ciicuit boaids, suffcient
iesistance and ductility aie of gieat impoitance. Coatings that have a tensile stiength of about 40 to 50
kg/mm
2
may be obtained at a tempeiatuie of 50 to 70C. Theii ultimate elongation, which chaiacteiizes
ductility, may be as high as 6 to 8%. Coppei coatings obtained at ioom tempeiatuie aie moie biittle.
Highly ductile coatings may be obtained only fiom solutions containing special additives. Ductility
incieases when deposited coatings aie heated in an ineit atmospheie at tempeiatuies of 300 to 500C.
Ni-P and Ni-B coatings aie ielatively haid; aftei deposition, theii haidness, which depends on the
amount of P and B, is 350 to 600 kg/mm
2
(3400 to 5900 MPa) of Ni-P coatings and 500 to 750 kg/mm
2
(4900 to 7400 MPa) foi Ni-B coatings, while aftei heating at about 400C, it is 800 to 1000 kg/mm
2
foi
© 2006 by Taylor & Erancis Group, LLC
í|ecrro|e·· P|oríng 27-11
Ni-P and 1000 to 1250 kg/mm
2
foi Ni-B. Hence, such coatings have the same haidness as that of
chiomium coatings. The tensile stiength of Ni-P coatings is in the iange of 40 to 80 kg/mm
2
.
The ductility of nickel coatings, if theii haidness is taken into account, is iathei high: theii ultimate
elongation is less than 2%. Such a combination of haidness, weai iesistance, and ductility is unique.
The electiical conductivity of chemically deposited coatings is usually lowei than of the iespective
puie metals. Resistivity of thin coppei coatings (0.5 to 1.0 m) deposited at ioom tempeiatuie is 3 to 4
1.0
-8
m - twice as gieat as that of puie bulky coppei. The suiface iesistance of such coatings is 0.03
to 0.07 /m Howevei, ductile coppei coatings that aie obtained at tempeiatuies of 50 to 70C have a
iesistivity of 2 10
-8
m, close to that of puie coppei.
The iesistivity of Ni-P and Ni-B coatings depends on the amount of nonmetallic component, and it
is usually in the iange fiom 3 to 9 10
-7
m; that is much highei than that of puie bulky nickel (0.69
10
-7
m). Heating causes ieduction in iesistivity.
Magnetic piopeities of the coatings of such feiiomagnetic mateiials as nickel and cobalt may vaiy
within a veiy wide iange. With an inciease in the amount of phosphoius in nickel coatings, theii
feiiomagnetism decieases, and coatings containing moie than 8 mass peicent of phosphoius oi 6.5 mass
peicent of boion aie nonmagnetic.
Coatings of Co-P, Co-B, and cobalt alloys with othei metals have highly diffeient magnetic piopeities.
These depend on the composition of the coating, theii stiuctuies, and theii thicknesses, and they may
be contiolled by changing the composition, pH, and tempeiatuie of electioless plating solutions. Usually,
cobalt coatings exhibit a high coeicivity (15 to 80 kA/m); howevei, soft magnetic coatings (0.1 to 1.0 kA/
m) may be deposited as well.
Optical piopeities of coatings aie less vaiied and do not diffei so much fiom those of puie metals.
Chemically deposited coatings aie usually dull; when special additives aie intioduced, biight coatings
aie obtained. Since they aie not used as fnish decoiative coatings, piopeities of appeaiance and biightness
usually aie not essential.
Silvei and gold coatings aie often used as miiiois, but the light-ießecting suiface is usually the innei
suiface, which is adjacent to the smooth glass suiface. Chemically deposited thin gold flms aie employed
as optical flteis; they pass visible light but ießect infiaied iays and iadio waves.
Chemically deposited coatings aie usually less poious than the iespective electioplates; theiefoie, they
piovide bettei piotection of the basis metal against coiiosion. Coiiosion iesistance of the coatings
themselves may be diffeient depending on stiuctuie and composition. Ni-P and Ni-B coatings aie moie
iesistant to coiiosion than nickel electioplates; this may be due to theii fne ciystalline stiuctuie.
Relerences
1. A. Biennei and G. Riddell, }. Res. Natl. Bur. Stand., 37, 31 (1946).
2. W. Goldie, Metallic Ccating cf Plastics. Hatch End, Middlesex, England: Electiochemical Publica-
tions Ltd., Vol. 1, 1968; Vol. 2, 1969.
3. F. Peailstein, °Electioless plating," in Mcdern Electrcplating, 3id ed., F. A. Lowenheim, Ed. New
Yoik: Wiley, 1974, p. 710.
4. M. alkauskas and A. Vakelis, Khimicheskaya Metallizatsiya Plastmass. Leningiad: Khimiya, 1984.
5. R. M. Lukes, Plating, 51, 969, 1066 (1964).
6. M. Paunovic, Plating, 55, 1161 (1968).
7. F. M. Donahue, Cberfüche-Surface, 13, 301 (1972).
8. A. Vakelis and J. Jaciauskiene, Elektrckhimiya, 17, 816 (1981).
9. I. Ohno and S. Haiuyama, Surface Techncl., 13, 1 (1981).
10. A. Vakelis, Elektrckhimiya, 14, 1970 (1978).
11. E. B. Saubestie, Plating, 59, 563 (1972).
12. K. M. Goibunova and A. A. Nikifoiova, Physiccchemical Principles cf Nickel Plating, Tianslated
fiom Russian, 1963, TT 63-11003.
© 2006 by Taylor & Erancis Group, LLC
27-12 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
13. G. Gawiilov, ChemischelStrcmlüse/Vernickelung. Saulgau, Wuit.: Eugen Leuze Veilag, 1974.
14. K. M. Goibunova et al., Fizikc-Khimichesklye Csncvy Prccessa Khimicheskcgc Kcbaltircvaniya.
Moscow: Nauka, 1974.
15. A. Molenaai and J. J. C. Coumans, Surface Techncl., 1õ, 265 (1982).
16. Y. Okinaka, in Gcld Plating Technclcgy, H. Reid and W. Goldie, Eds. Hatch End, Middlesex, England:
Electiochemical Publications, Ltd., 1974, p. 82.
© 2006 by Taylor & Erancis Group, LLC

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