260 ELECTRODEPOSITION OF LEAD AND LEAD ALLOYS

0.2 V. Acidic electrolytes based on tetrafluoroboric acid, TABLE 8.10 Electrolyte Composition and Working
sulfamic acid, and perchloric acid as well as solutions Parameters for the Lead Dioxide Deposition
containing complexing agents and weakly acidic and alka- Lead nitrate, Pb(NO3)2 350 g L
1
line electrolytes were all investigated. Brenner describes a Copper nitrate, Cu(NO3)23H2O 20 g L
1
number of electrolyte formulations [55]. There are some Substrate for the anode Titanium
further references to such electrolytes given in more recent Cathode Copper
literature, including those electrolytes that use complexing Electrolyte temperature 60 C
agents such as tartrates [81], diethylenetriamine pentaace- Current density 4–8 A dm
2
tate/gluconate [82], diethylenetriamine–pentaacetate [83],
and polyethylenepolyamine [84].
For other applications, deposition of lead dioxide can be
Eastham compared the properties of lead–indium and the
made on suitable substrates, especially titanium [90] or
ternary lead–tin–copper alloys as wear-resistant coatings for
graphite [91]. The valve function of titanium during anodic
bearings [85]. He found that the lead–indium layer has a
polarization is prevented either by deposition of thin layers of
higher fatigue strength but a lower wear resistance compared
platinum or palladium or by addition of fluoride [90] to the
with the ternary alloy.
electrolyte. The electrolyte is normally a solution of lead
There is still some production of lead–indium alloys for
nitrate and copper nitrate. The addition of copper is made to
steel-backed silver–lead or lead–bronze bearings. In such
prevent unwanted cathodic deposition of lead. Table 8.10
applications the lead–indium layer is still produced by
shows a typical electrolyte composition and the working
plating the two individual layers and diffusing [86].
parameters for the deposition of lead dioxide [92].
The combination of the cathode and anode reaction leads
8.5.9 Lead–Cobalt and Lead–Nickel to a liberation of nitric acid. In order to keep the metals in the
solution and the pH constant, the addition of lead oxide, PbO,
A U.S. patent [87] refers to the deposition of a cobalt– and copper metal is recommended [92]. Investigation into
nickel–lead alloy onto aluminum. The function of this de- the formation of stresses in electrolytically deposited
posit is to enable the aluminum parts to be welded with each lead dioxide layers were reported by Gnanasekaram and
other or with other metals. The electrolyte used for such co-workers [93]. The existence of internal stresses can lead
deposition is a citrate-based electrolyte at pH 10.5. to cracks in the anodes and thus can have an adverse effect on
Investigations into the magnetic properties and the struc- the stability and the shelf-life of the anodes. The operating
ture of cobalt–lead alloys with 20–70% Co were described by parameters of the electrolyte must therefore be carefully
Surzhko and Korolinko [88]. A pyrophosphate electrolyte controlled.
with tartrate and citrate as complexing agents operated at pH
9.7–10 and 60 C was used to deposit the alloy.
The influence of thiocyanate ions on the deposition 8.7 DEPOSITION FROM NONAQUEOUS
of nickel–lead or cobalt–lead alloys was investigated by SOLUTIONS
Franklin and co-workers [89]. The thiocyanate ion catalyzes
the deposition of the transition metals with a corresponding Investigations into the deposition of lead alloys from non-
higher rate of codeposition in the alloy. aqueous solutions were made for those metals that cannot be
plated from aqueous solutions because of their negative
standard potential.
8.6 ELECTRODEPOSITION OF LEAD DIOXIDE
8.7.1 Depositions from Aprotic Solvents
Electrodeposition of lead dioxide is of commercial impor-
tance because it is the method used for the production of lead Deposition of a wide range of lead–aluminum alloys from
dioxide anodes. PbO2 has a high electrical conductivity organic solvents is described in many papers. Alloys with a
(0.5  104 V
1) and a high overpotential for the production lead content of 32.6–99.3% have been plated from an elec-
of oxygen. Such anodes are therefore used in many technical trolyte based on ethylbenzene/toluene with AlBr3 (3 mol
applications (production of zinc by electrolysis from elec- L
1), tetraethyl ammonium bromide (0.5 mol L
1) and lead
trolytes containing sulfates, persulfate production, etc.). in the form of lead tartrate. The molar ratio between alumi-
Lead can be used as anode material. During anodic num and lead has to be greater than 100 [94].
polarization the lead surface passivates and forms lead In an earlier publication the same authors investigated the
dioxide. The lead for the reaction comes from the underlying deposition of aluminum–lead alloys from benzene, toluene,
layers of lead. If lead anodes, which contain 1% silver, are or ethylbenzene electrolytes with AlBr3, PbBr2, and tetra-
used as the starting material, the lead dioxide anodes sub- ethyl ammonium bromide or KBr as conducting salts. Lead
sequently produced will be extremely stable. deposition is favored (90–95%). To achieve alloys with a
 REFERENCES 261

higher aluminum content, the lead concentration has to be of adsorption of the metal ion onto the surface of the base
limited to a maximum of 0.005 mol L
1 when the Al con- metal. Investigation into the UPD of lead has been made on
centration is 2–3 mol L
1. It is also possible to complex the silver or gold substrates. Besides theoretical investigations to
lead by addition of tartrate [95]. study the phenomenon itself, experiments were carried out in
The anodic dissolution of aluminum–lead alloys in elec- an attempt to modify the catalytic properties of gold electro-
trolytes based on AlBr3, PbBr2, and KBr was investigated des by the adsorption of lead layers for electrochemical
using cyclic voltammetry [96]. Investigation into the reductions [104, 105].
cathodic deposition by cyclic voltammetry shows that the The UPD of lead onto stainless steel was examined
potential difference between lead and aluminum in ethyl- [106, 107]. It was discovered that the evolution of hydrogen
benzene electrolytes is only about 300 mV, compared to on the cathode and thus the adsorption in the steel (known as
1.5 V in aqueous solutions [97]. hydrogen embrittlement) could be considerably reduced.
It is not possible to plate aluminum–lead alloys from Underpotential deposition is a process which is different
electrolytes based on A1C13 and LiAlH4 in tetrahydrofuran from the objectives of the lead deposition in the conventional
or diethylether, which are the electrolytes used for deposition meaning of electroplating. A detailed discussion of this
of aluminum [95], Capuano [98] gives a review on the process is beyond the scope of this text.
electrolytic deposition of Al alloys with specific reference
to the use of plating technologies such as pulse plating and
8.9 APPLICATIONS OF ELECTRODEPOSITED
barrel plating.
LEAD

8.7.2 Depositions from Molten Salts The main applications of electrodeposited lead are a result of
corrosion-resistant properties against such corrosive chemi-
Deposition of lead–calcium alloys from molten salts based
cals as sulfuric acid, chromic acid, or phosphorics acid. In the
on mixtures of CaCl2–CaF2–PbCl2 has been described in the
atmosphere several corrosion products, mainly carbonates
literature. Deposition of calcium is favored from such mix-
and alkaline carbonates, form protective layers that prevent
tures, since the concentration of lead in the mixture is limited
the underlying metal against further attack.
to 3–5% by weight [99].
A huge field of application of electroplated lead is in the
Production of a lead–calcium alloy by using molten lead
production of lead accumulators. All the parts that come into
as the cathode and depositing calcium on this from a molten
contact with sulfuric acid are plated with 200 mm lead. The
salt mixture of CaCl2–CaF2–CaO at 750 C is referenced in a
base material is most usually copper, but there is also
Japanese patent [100]. A similar reaction for the deposition of
reference made to the use of aluminum because of the weight
a lead–zinc alloy that involves the deposition of zinc from a
reduction of the components [108].
mixture of LiCl–KCl–ZnCl2 at 400 C has also been de-
Lead is a superconducting metal with a jump temperature
scribed in the literature [101].
of 7.2 K. The use of electrodeposited lead layers for applica-
Ternary alloys of lead such as K–Na–Pb, Mg–Na–Pb, or
tions in the field of superconductivity is described in the
K–Mg–Pb can be deposited from molten salt mixtures of
literature [109–111].
Na2CO3, KCl and NaCl [102], NaCl/MgCl2, or KCl/MgCl2
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