Maler~al~ Chemistry and Physics, 25 ( 1990) 439- 46 I

439

REVIEW

,PULSE PLATING

G. DEVARAJ
Central

and S, GURUVIAH

Electrochemical

Research

Institute,

Karaikudi

623 006, (India)

S.K. SESHADRI
Dept.

of Metallurgical

Eng., I.I.T., Madras 600 1l36 (India)

ABSTRACT
The review
pulse

extensive
etc.

of

platinq
work

has

were

literature

initially

available

was

on other

also

been

also extended

used

to

on pulse
plate

plating

copper

metals

such

as nickel,

Apart

from

single

done.

to plating

numerous

and

attempted.
survey

the

chromium,

metals,

alloys

has been
gold,

palladium,

the

pulse

of nickel,

Though

shows
zinc,

plating

chromium,

that
silver

techniques

gold,

palladium

etc.
Developments
use of pulse
amorphous
current
this

that
plating

alloy
on

paper.

have

taken

place

in the

areas

like

and semi-conductor

surface

roughening

This survey

the

anodising,

plating.

and

also includes

during

other

last

three

deposition

morphological

include

of composite

Mass transport

the theoretical

decades

effects,

materials,

effect

effects

aspects

are

the

of pulse

presented

and mechanism

in

of pulse

plating.

INTRODUCTION
Pulse

plating

has emerged

In the

conventional

direct

namely

the

density,

three

current

variables

ip (2.1 current
constitute

that

are

on time

one

pulse

as a new technique
current
which

of primary

can

Some

there

be varied.

importance.

and (3) current

cycle.

for deposition

electrodeposition,

in pulse

The

relationships

sum

of

used

one

and alloys.
parameter,

methods

They are (I) peak

off time.

important

But

of metals
is only

on

we have

current
and

in pulse

density,

off

plating

times

are

as follows:

Duty cycle

on time

x 100

on time + off time

0254-0584/90/$3.50

0 Elsevier Sequoia/Printed

in The Netherlands

440

Average
similar
and

current

to that

on-off

a given
plating

number

average

has

been

Usually

established

pulse

nucleation

decrease

higher

plating

higher

rate

rate

until

to

beneficial

of

are

pulse

current

densities

pulses

1 to 100%

are

we have

for obtaining

generally

used for

of square wave PuISes, as shown

densities

a finer

grained

have

deposit

beneficial

formation

with

pulse depending

effects
and

as the

d.c. density.

the

deposition

in electronics

more

recently

expensive
have

of

include

finer

pulse

effect

current

This results

grains.

Current

on the nature

reduction

improvements

on

[1,4,5,6]

in

density

in an increased
efficiencies

may

of the electrochemical

in porosity,

low inclusion

mechanical

effects

been

in the

last

rectifiers.

in

single

The

electronics

metals

technique

amorphous

1141. Theoretical

international

mainly

of

plating

two

d.c.

and

level,

physical

aspects

decades

[15].

as alloys

Pulse

alloys [Iz],

Interest

subject

Though

can

techniques

semiconductor

in pulse

of pulse

by application

plating

techniques

this

continues

of this technique

be carried

also find

plating

have also been extensively

symposia held between

Work on this interesting

as well

[9,10].

of pulse wave rectifiers.

application

industries.

have also begun to benefit

by this

role in anodising [II],

have lead to the introduction

than

industries

Electrodeposition

beneficial

SINGLE

wave

of combinations

from

is

etc.

to be so, other
[7,8].

vary

density

[2,3].

yields

or increase

Developments
These

may

current

So, in pulse plating

pulse current

square

than the corresponding

leading

Other

properties

that

of electrodeposits

is considerably

reactions.

of different

a variety

average

cycles

milliseconds.

Simple

density.

The

could also be employed.

the properties

either

Duty

to

of combinations

though

cycle.

electroplating.

microseconds

current

operations,

in Fig.1 [I]
It

from

= ip x duty

ia

used in d.c.

times

an unlimited

density,

out with

an important

[13] and composite

investigated

and reported

was demonstrated

by three

1979 and 1986 [16,17,18].

is reviewed

and presented

in this paper.

METALS

Copper
The

surface

producing

finer

structure
grained

of

a single pulse by consuming

deposition
rapidly
with

from

than d.c.
low

pulse

sulphate

was

with

current

those obtained

baths

periods

of

0.1

the microstructure
by d.c.

deposition

by pulse plating

ness with

copper

deposition

improved

Also

using

pulse

reduction

current

of copper

passed through the electrodes

and

by

ion during

1191. Copper

produced

micrograined

deposits

far

Lamb [Zl]

observed

in copper

deposition

to

50

was low. Despic

that

microseconds

and hardness were

it was observed

at very

by

the complete

all the current

based

deposits [ZO]. However

as high as 10 A/dmL,
from

copper

structures,

that

with

current

efficiency

and Popov [22] observed

low frequencies

current

not significantly

more

densities
different
for copper

a surface

rough-

(IO cps), but at higher frequencies

441

ON

OFF

ilJ--ik

.h-UL

SUPER IMPOSE0

PULSE
FT,

--+Tt

PULSE

-I

TON (1)

f
DUPLEX
T0)1

--

TOFF !- +

0-v

OFF

PUL SE0

PULSE
1

-It=-.
TON tC)

_L

UdL

#L

TON(A)

l-u

.-J

PULSE

PULSE

ON PULSE

PULSE

REVERSE

TOFFh)
TffFU

Toli~cl

1r
r.

OMtA

Y/-if

PULSE REVERSE
OFF

Fig.1.

WITH

PULSE0

TIME

Different

forms

of pulse

III.

PULSE

REVERSE

442

(TOO00 cps)

smooth

was

very

thin

at

so closely
ties

got

that

depending
their

off

big

good

deposition

grains

of

pulse

et

al,

[32}.

to vary
actions

An

Cu+ + eDuring

this

AES

80.4

by

the

diffusion

profiles

of

the

layer
surface

are even and no irregulari-

Holmbom

and

Jacobsson

and

an

increase

that

grain

size

as well

copper

though

and

surface

of

to pause

observed

macrothrowing

[30].

power

roughness,

Popov -[[28,

morphology

on pulse

were

of

frequency.

copper

ratio.

deposits

With

Levelling
was

291

ionger

was

poor

for

found
copper

,sec

TIME

the

current

has been
report

with

under pulse conditions

efficiency

ascribed

[333 found

to 93.7%

__),
-3

the

copper

formation

current

pulse current

are represented

for

to the

deposition
of

efficiency

C311.

cuprous
for

as shown in Fig.3.

interval

less

in

deposition

The cathodic

re-

as

cut

in the bath.

was

ions by Wan

copper

(1)

cu

the first

ions accumulate

observed

of pulsing

deposited

in copper deposition

Cu++ + e-

also

plating

earlier

and

from

deposit

obtained

power of copper deposition

mentioned
plating

were

because

micro

acid baths [31] (Fig.2).

Fig. 2. Throwing

As

and the resulting

[27]

observed

Off

pulse

was
the

[23-2&J

frequency

with

from

This

and followed

results

Despic

also

on the

time,
be

obtained.

on the square root of the reciprocal

studies

depended

to

and

linearly

flux

Similar

investigators

Savic-maglic

were

frequencies

the diffusion

amplified.

many other

in

deposits

high

(2)
of pulsing,

reaction

1 is greater

than reaction

2 so cuprous

443

PULSE

TIME J set

92

I-

,_

r,
I-

82

80IL

I
0-l

O-05

I
O-15

0.;

OFF TIME, set

Fig.
3. Current
plating
C33J.

In

addition

used
less

efficiency

for
stress

inclusion
reverse

to

copper
in
in

square

the

and

circuit

plating

pulses,

which

deposit

was

copper

wave

deposition

printed

current

of

pulse

resulted

more

board

advantageously

as a function

in

ductiiity

as
In

plating.

reverse
finer

of

off

plating

grains,
well

as

eiectroless

time

during

techniques

doubling

the

reduction
copper

were
plating

[341

of

solution

pulse

also
rate,

hydrogen
aIs0,

pulse

used [35].

Gold
In
has

generai

pulse

plating

compared

the

porosity

evaporation,
the

pulse

plates.
in
the

direct
technique

Films

porosity
decreased

formed

reduced
of

current

plating,

deposits
and

[Fig.4].

Evaporated

by d.c.,

asymmetrica.c.

depending
porosity.

on

thickness.
Pulse

current

in gold

porosity

gold

deposits

obained

asymmetric
films

from
alternating

appear
and pulse

Grain

refinement

produces

very

[4,36,3?].
various

to

have

more

was
much

like
with

finer

pores

exhibited

primariiy

[38]

plating

current

techniques

Rehrig

techniques

than

responisble
grains

d.c.

variations

than

for
d.c.,

1.5

3-o

L-5

6.0

THICKNESS,
Fig.
4.
Electron
Pulse

Relationship
between
porosity
and
gun evaporation,
6:
Asymmetric
plating

because
the

of

was

of nucleation

reported

by

and

deposition

[31,
density

current

and
of

grain
of
and
in

the

adions

current

current

efficiency
electrolyte.

reported

et

With

thickness
of
a.c.
plating,

start

[39-411.

al.

also

[43]

after

gold
C:

each

the

films
Direct

pulse,

based

deposited
plating

thus

found

to

greatly

bright

Bright

by Yamashika

but
laminar
and

Ito

in

this

and

was

duty

and

results.

bath.

improved

deposits
[45].

gold

by
and

A:

D:

increasing

of

less
current

with

be

authors

an increase
with

pulse

peak

the

du-

50%

the

and duration
of adatoms

Jacobsson

obtained

also

lower

than

diffusion
and

gold

average

with

peak

Holmbom

gold

At

peak

of

constant

cycles

could

The

at

lower

power

increased

surface

electrolysis

pulses,

deposits.

growth

deposits

the

pulse

fast

pulses

to the

transfer

gold

of

of

of
grain

by

microthrowing

forms

proportional

charge

any brighteners

of deposition

the

experimental

that

the

30

current

deposits

combination

structure

66%,

peak

on

gold

improved

grain
than

higher

of

imposed

to be inversely

correlated

using

of
also

pm

adhesion

bath

greater

found

experiments
without

the

the

Mechanisms
were

and

observed

pulse.

which

Knodler

of

cycles

was

peak.

their

and

Rehrig

and

duty

sites

power

Raub

421.

diameter

the

10.

sites.

agitation

current

ration

nucleation

microthrowing

currents

9.0

1381.

new

number
Better

7.5

with

observed

1441
pulse

lower

in temperature
current

were

445

Dini

and Johnson [46]

current,

pulse current

and yield
current

strength

by a pulse current.

under

lower.

their

a diffusion

The

in deposits

in micro

experiments

for

suitable

model

results

current

This was

be improved

obtained

Ductility,

by direct

tensile

obtained

with

strength,
alternating

hardness and contact

resistance

found

that

corrosion

resistance

of

with pulse current.

Cheh [51] developed

current

to

improvements

[SO] in

gold deposits improved

applied

found

of gold deposits

electrolysis.

were reporte~[47,48,49].

Arumaki

taneous

current

However,

with pulse current

and

the properties

were

electrolysis.

Waki

compared

and alternating

to calculate

indicate

deposition

although

limiting

confirmed

overall

for

of deposition

the magnitude

can be considerably

the

conditions,

experimentally

that

the rate

higher

of metals

of the instan-

than that

plating

rate

of direct

in general

gold

deposition

from

various

grain

refinement

but this metal

was

typesof

bath.
Thorium
to

be

is added

pulse

current,

while

reviewing

in the

the

anticipated

rectifiers

in the

base metal

gold plating

gold

amount

the

Plating,

and

in gold plating

incorporated

of

papers
that

baths

deposit

thorium

presented

increasing

microsecond

Thin

with pulse current

decreasing

is reported
in the

wifl

film

bondability.

to be controlled

AESF

commercial

range

depositions.

for

thereby

International

availability

lead

to

the

have been produced

[52).

Reid

Symposium

of suitable

development

chokes and antennae

for

[53],

on Pulse

pulse current

of both

laser

seems

By applying

precious

radiation

using

by Bhar and Lamb 1541.

Nickel
Pore
with

free

contained
tion

fewer

in porosity

However
in

Ni

frequencies

if

porosity

power,

deposits

was

from

obtained,

substrate

was not well

Sutter

and

reduction

current

deposits

in tensile

were
from

stress

and Landolt
solutions

density

is higher

pulsating

chemical

[hOI

obtained

by p&e

nickel

nickel

deposits

deposits

a reduction

pulse.

crack
amide

alternate
with

[56].

in microthrowinq

with

from

was associated

scale reducprepared

produced

in brightness,

bath using periodic

which

well

improvement

an improvement
for

was

pulse current

reported
of

on an industrial

surface

current

smooth deposits

By

coatings

baths

[57,58].

current

change

using

free

showed

in grain

size

[59].
their

that

influences

dissolution

dissolution

current

and surface

the

prepared
also

porosity

obtained

in

were

However

when

an all chloride

in pulse

current

in

of deposits

observed

machining

[36]

technique

about 100 to 5 grain/pm*

Datta

thickness

It has also been shown that

even

deposits.

nitrate

of

not

of

Ni deposits produced
a drop

microns

the

hardness

ductile

10

pores than rough deposits [55].

the pulse reverse

and

of

of IO4 cps at 2 A/dm*.

than
the

d.c.

study

Also

~transpassive

finishing

of

efficiency

operations.

they

nickel

for

have

dissolution

electrodes
given

in sodium

average

indicated
behaviour

that
in

current
the

use

electro-

446

Chromium
It

has

power
[61]

been

of

reported

chromium

reported

cycles
Also

the

10

Colobini
current.
was

[62]

also

at

lustre

by

the

crack

of deposits

was

found

is also
sites

begins

resistance

is

observed.

of

pulse

plated

1501.

of

with

further
is

chromium

found

deposits

from

in

that

possible

was

with

oxygen

pulse

reverse

chromium

For

selecting
thickness

frequency,

loss

the

be

duty

critical

formation

cause
to

and

free

the

increase

Zhang

and

deposition.

current.

of

suggest
a

and

as a depolarizer.

Crack

pulse

covering

sec.

pulses

acted

deposits

knowledge
With

chromium

current

with

and

Tanchin
to

obtained.

[63]

interruption

power

msec.

chromium

prior

[64]

0.1

increased

were

essential.

They

each

be

of

Hoey

that

solution
of

as pulse

deposits

and

insist

after

to

uniformity

throwing

efficiency

higher

harder

Saidington

authors

formation

nucleation

deposits

and

acid

pulses

coulombic

were

greater

free

with

the

efficiencies

observed

deposited

Corrosion

chromium

improved

chromic

plating

reduced

of

crack

pulses,

which

aus

size
evolution

Also

suitable

100

current

from

chromium

to

grain

and hydrogen

pulsed

deposition

that

from

that

for

of numer-

loss

better

of

in

than

Iustre.

for

d.c.

[35].

Zinc
Pulse

current

whereas

direct

cies

pulsed

zinc

were

The

adherence

The

risk

produced
current

current

produced

by pulse

varied

with

hydrogen

deposition

from

and pulse

length

zinc

black

produced

obtained

of

smoother

porous

rough
current

from

current

density

embrittlement

alkaline
[69]

of

was

deposits:

Zn

alkaline

found

[68]

for

to

at low

Zn

with

bath

efficiency

pulse

of

batteries.

in the

current

decrease

frequen-

deposits

use in storage
of

and

solutions

Adherent

concentration

reduced

zincate

however

[22,65,66].

solutions

and

was

electrolyte

(Fig.

massy

deposits

alkaline

[67].
of

current

Zn

density

5).

Silver
The

capacity

current

[70].

obtained
were

by

ammonia
of

resulted

Silver

and

critical

based

nitrate

which

baths

ing to Hosakawa

silver

silver

by
et

[72]

--et

al.

where

might

produced

stable
smooth

electrode

al.

[73]

the

different

[71].

Fine

baths

described
the
to
rate

crystallite,
and coherent

was

with

the

leading

accelerate

the

et
from

increasing

overpotential

of

oxide
particles

Pavlovic
al.

Hayashi
baths

increased

radius

the
of

reported

thiocyanate.

an

of

shapes

Hossokawa

electrode

the

charging

as

by

ammonia
in

the

in

pulse

obtained

lysis

on

of
Different

a
of

thus

grained
on

pulse

of silver

electroon

time

concentration

due
fine

be

deposits

in the

and

nucleation

deposits

silver

adatom

favouring

pulse

can

ethylenediamine,

situation

current

higher

by

properties

based

this

peak

improved

to

grain
with

decrease

formation.

pulse

accord-

et al. [74].

Palladium
Pulse
and

no

current
significant

was

used

for

improvement

palladium
was

deposition
noticed

from

compared

nitrate
to

d-c.

based
plating.

electrolytes
However

447

PULSE LENGTH , msec

Fig. 5. Influence of pulse length on curr$nt efficiency
for zinc deposition
zincate baths at current densities,
A/dm : o 2, A 5, 010 [69].

coatings
moto

of less

lrodiamine
current
was

baths

2.5 microns

not

were

obtained

in crack

that

longer

during

lower

[74,771.

Other

with

noticed
of

in detail

and found

densities

deposits

bath

than

et al. [76] studied

for

Pd

free Pd deposits

found

fine

the

to be crack

off

time.

deposition

deposits

and shorter

content

from

of (NH4&HP04

were

free

obtained

off times.

However,
than

and pore

[751. Fuku-

of Pd from dichl~rodinitro

grained

on times

hydrogen

Additions

were

the deposition

from alkaline

obtained

an ethylene

with

diamine

and benzoic

acid

of 50-100

A/dm

with high pulse

Desarption

a dinitrodiamine

were

and dichio-

of hydrogen

bath
d.c.

resulted

Similar

palladium

(If) complex

in PdC12 solutions

resulted

with pulse [78].

Metals

Use

of

of cobalt

pulse
than

[25] produced

current
obtained

finer

in the
with

grained

range

d.c.

due to grain

deposits

of cobalt

refinement
from

produced

harder

(Fig.61 [79,80].

sulfamate

solutions

deposits
Cavallotti

with

greater

uniformity.
Bright,

smooth

farmamide

baths

from

in

results

1 to 5% [81].

and fine
with

pulse

grained
current

deposits
density

of tin were
of

produced

10 mAfcm*

from
with

NN dimethylduty

cycles

448

PULSE CURRENT,AMm2
Fig. 6.
density

Strength
and hardness
from Watts electrolyte

Popov

[82]

increased
ratio

in

his

rapidly

at

of I:1

In

studies

pulse

reported,

current

that

density

as a function

the
of

microthrowing

10

mA/cm2

of

pulse

power

with

current

of

cadmium

a pulse

to

pause

to 1:9.

aluminium

densities

SEM

of cobalt
electrodeposit
at pH 2 and 40C 1801.

electrolysis

could

be

increased

from

molten

more

than

aluminium
in

the

chloride

baths,

conventional

the

electrolysis

current
with

d.c.

1831.
In

rhenium

ciency

was

plating

much

Improvement
resistance

PULSE

rate

of

to

carbon
a Cr

The

layer

with
ratio

be

was

increased,

also

used

producing

for

with

could

experienced

components
pulse

by

current

pulse

Hosokawa

et

than

d.c.

plating

of 0.11

APPLIED

and

current.

danger
be

with

hardness,

of

enhanced
Ni-Co-Zn

[84]

rhodium

that

in
by

porosity
Miu

to eliminate

for

burning

avoided

and

alloys
desorption

and

in

Fung

contact

1851.

in the

aluminium

quarternary

was

effi-

Also

deposits.

COATINGS

anodising

Modulated

hydrogen

current

and

cracks

[11,62].

composite

the

plating.

MISCELLANEOUS

used

anodized

Ni-Co-Cr-Zr

of

TO

al.

reduction

was found

advantageously

anodize

authors

fibre

pulse

TECHNIQUES
can

oxidation

successfully
[86].

observed

reported

efficiency,

to current-off

current

difficult

with

current

CURRENT

Pulse

was

higher
in

were

a current-on

it

also

where

alloys

pulse

on composite
from

deposited

that

currents

the
first

the
are
were

materials
surface

of

followed

by

449

Cobalt-aluminium
with
with

Au-Co

reduced
The
the

mechanical

alloy

the
grain

films

fully

Laminer

from

metals
pulse

areas

on

by
the

metals

cm

and Cu-Ni

and

between

it

also

Au

usinq

of

reported

that

pulse

hiohly

hitherto

[IZ].

current

codeposition

the

pulse

methods

current

using
alloys

electrodeposited

conductinq

pulse

current
harder

the

with

data

on

d.c.

of

success-

materials

with

were

as shown

increased

characteristics

difficult

However

platino

pulse

alumina

[87].

and Sn are

and

deoosited

and pulse

was

potentio

amorphous

Weinroth

d.c.

case

photoelectrochemical

like

wires),

deposited

the

particles

semiconducting

(OJO3

Lashmore

baths,

observed

nickel-phosphorous

difference

In

alumina

improved

[SF?]. Also

of Cu-Pb

by

films

successfully

[14,801.

cyanide

and

current

plated

as reported

Cd-Te

produced

small

were

of suspended

pulses

pulse

extreme1.y

a small

of

of

thus

with

The

plating

size

also

properties

codeposition

frequency

the

composites

improved

over

olatinq

[13].

[l391.
than

d.c.

deposits

wear

showed

only

nickel-phosphorus

alloy

[12].

in Fiq.7.

0 12P.PULSE
AS

PLATED

HEAT TREATED

a\ SP, ELECTRO

HARDNESS , KHN
Fiq.7.

Wear

The

to

function

content

deposits

extended

of nickel

as

phosphorus

amorphous
was

rate

were

in the
also

electroless

and cobalt

of

production

Knoop

alloy

produced
copper
[35].

hardness

could

be increased

by pulse

and

nickel

for

methods
deposition

with
[90].
and

pulse.
Also
thin

Microcrystalline

this

new

layers

technique
[2-300

nm]

450

DEPOSITION

OF ALLOYS

Nickel

were

alloys

vements
have

in alloy

been

Ni-Fe

deposits,

noticed.

alloys

with

pulse

[50,91].

wear

and

ailoys

Ni-Sn

that

Malone

for

Ni-Mo

of

5A/dm2.

stress
[97]

and

however

alloys

with

improved

mechanical

roughness

of

and

pulse

alloy

properties.

MO at

circuit

were

possible

with

The
Ni-Zn

They

have

with

pulse.

to get control-

higher current

pulse.

for

[IZ].

[94].

an average

deposit

are

were

be controlled

with

Corrosion

deposits

resistance

and Raub

switching

in the

alloy

of hard chromium,

can

obtained

was reported

and Weinroth

reported

15-30%

alloy

corrosion

to that

etal.96)

were

Ni-Cr

by Raub

in the

increased

Ni-Cu

of

anode current

deposits

structure

by Lashmore

was comparable

containing

free

and grain

compositions

Cherkaoui

MO current

hardness

of

inclusion

alloys.

crack

the application

as reported

studied

density,

surface

deposits

a new automatic

cy

current

to those found in the case of single metal

deposits

also

of Ni-Co

Also

Impro-

d.c.

particles

[95] described

of pulse electrolysis.

range

with

were

foreign

CURRENT

with

in composition

wider

than

led composition

peak

similar

of Ni-Cr

plating

PULSE

studied

Uniformity

192-931

dry sliding

reported

WITH

widely

efficien-

current
With

reduction

resistance,

density

increase

in

in internal

brightness

and

by pulse electrolysis:

improved

dependent

on the

composition

of

the alloy [98].

It

has been

and

tensile

unaltered

reported

strain
whereas

density

stability
are

of

against

essential

in the

that
19
IO

alloys

in the
pores

pores

showed

per

were

of

applications.

properties

of Au-Ag

showed a decrease

a satin

was

cm3

These

pulse

observed
to

Hz

in grain size, coating

hardness

for

obtained

with

increased
Au-Ni

[991.

with

using TEM.

Mausli et

pores

Smaller
high

was

about

grains and

hardness

and

by using pulse current,

et al. [loll

deposits

of

appearance

deposition

be responsible

with

was

appearance

bright

properties,

alloy

The

alloy

Catonne

at IO-600

current,

deposits.

Au-Co

considered

shocks.

[IOZ]

alloy

case

contact

by Metalov

use of

gold

thermal

for

physical

deposited

by the

for

Au-Co

al. [IOO] reported

?i-A dia and about
a high

that

reduced

experienced

improvement

pulse current.

pulse current

density

roughness and nonuniformity

Au-Ni

of 5-200

alloys
A/dm

in grain composi-

tion.
Eckler

et

al.

[I031

pulses of 3 msec.
increased
that

content

on and

identified

pulse
of

the

in a Cr-Co

off

times.

alloy
et

was

al. [105].

With

and a fine
alloy

was

deposited
They

grained
distinct

Cr-Mo

alloy

times.

They

MO content

the phases produced

Zn-Ni
Nevov

on and off

and also a higher

Co

the

studied

alloy
the

coatings
found that

in the alloy.

deposited

help

of

with

X-ray

from
wear

a chromic

acid bath

resistance

of the deposits

Gelchinski
pulse

can

diffraction

with

et ai. [1041 observed

be varied

studies

by changing

the

authors

also

with pulse deposition.

with

pulse

have observed
structure
from

with
that

from

a higher

ammoniacal
Ni content

chloride

d phase of the alloy.

obtained

with

d.c.

It

electrolyte

in the alloy

(Fig.81

The overall

has also

been

by
with

structure
reported

451

20

e
t
F
;

16

Z
._
Z

12

I
2
I
40

I
6

. 4..,
I a, A/dm
80

J
160

120

iP , A/dm
Fig.
0.25

8. Effect
of
msec. and off

that

hardness

electrolysis
The

pulse
A

and Cheh

Smooth

and

with

pulse

also

been

order

grains
transport
verified

the

that
[IO01

corrosion
and

from

by

[I101

surface

[IIZI.

Tannerberger

and Pd-Ni

preferred

also

alloy

alloy

deposition
and
deposit

low

wa!j

at

Cu

and

orientation

Based

on

[113].

increase

times,

by

pulse

frequency
of Pb-Sn
was

[97,107]

alloy

alloy

[106].

reported

Pb-Sn-Cu

the

based

at

by

deposi-

IO

Hz

was

The

in average

current

alloys
curves

predicted

change

current

in

were

[109,

alloys

pulse

Pd-Ni

alloy

bath

Pd-Ni

polarisation

current

case

of Pd-Ni

of

for

on

fre-

smooth.

increasing

reported

at

improved

pulse

pulse

of
in

content

C12.NiS04

with

with
case

of

compact

be

Hz

in the

in the

hydrogen

deposited

can
100

alloy

content

by pulse

Schindler
with

alloy

the

[IO81

al.
the

alloys

experienced
in

Pd(NH3j2

resistance

smoother
in Pd-Ni

the

also

found

with

Zn-Ni

Pb

et
in

were

deposits

electrolysis

[I 111

91. Sata
increase

deposits

bright

observed

Improved

(Fig.

overall

of

Zn-Ni

electrolyte

was

amount

of

of

based

electrolysis

higher

[IO71

an

Also

quency.

Au-Ni

of

observed

corrosion-resistance

a sulphate-chloride

deposition.

Cheng
tion

and

of

benefit

alloy

current
on nickel
content
time 4.75 msec. [105].

1 IO].

changed

the

density

It

has

in

the

density

in addition

and

obtained

model

[I 1 II.
to

for

finer
mass

experimentally
metal

was

ratio

for

reported

452

30

20

8tl

60

Pb IN bath
Fig. 9.
* 0.4,

Variation
A 0.7,

of
0

and

long

with

improved

off

tion with
by d.c.
was

pulse.
[115].

with

Wessier

deposit

By

single

the

above.
cathodic

Current

[116].

[I171

OF
[I181

polarisation

duty

[114].

was reported

of the

alloy was lower

on the

d.c.

has observed

They

cycles:

the

High

than

n 0.1,

short

on time

Ag

for Pd-Ag

cathode

that

pulses

PULSE

content

alloy

for

that

potential

deposiobtained

Cu-in

composition

of

alloy

the

alloy

Ag

the
cold

time
of

Aq3Sn

effect

adsorption

curves

short

by

using

times

of

which

pulse

500-200

is more

currents
msec.

of
The

ductile

1.5
alloy

and posses-

deposits.

worked

mechanism

vs
-*

off

PLATING

observed

transfer

density

pure

alloys

and

compound

than

and

have

Ag-Sn

msec.

studied

polycrystelline

potential

5-100

intermetalIic

ASPECTS

charge

different

efficiency

a pulse
He

at

was high and extremely

no diffusion

produced

of

resistance

Hampson

potentials.
step

density

the hardness

on times

tarnish

crystal,

two

about

deposit

potentials.

Gluman

contained

and

current

superimposing

with

TtlEORETIC.AL

pulse

However

cathode

sed superior

Farr

brought

by Lokande

and

3 A/dm

though

alloy

roughness and current

deposited

varied

to

time

,%

lead in lead-tin
= d.c. (1071.

to be less pronounced

LO

was
were

duration

of

various

sheet

on

of

by

measured
sec.)

the

substrates

exchange

intermediates

proposed

(0.155

zinc

the

such

current

at

the

authors

to

electrodes.
expiain

by Tvarusko(119jat
on

stationary

as

using

the

various
and

moving

453

wires

in

speeds.
wire

copper

speed.

tion

that

enerqy

current

al.

expressinq

the

equation

in their

So

in

formation

of

et

surface

at

with

al.

curves

and

116

to

lower

[I211

in

roughness

too
of

be deposited

and

porosity

of

Cu

small-

the

same

IO5

Hz,

mV

for

200
the

derived

in

deposi-

a 40%

consumption,
study

with

with

overpotential

eneray

wire

at

overpotential

another

with
varied

copper
at

electrolysis

mV

current

varied

these

potential

can

overpotential

that

addition

Popov

quality

an

equation

deposition.

The

MD(Co-Cs)
.-

= protrusion

hoexp.

= pulse

r+l

p62
heiqht

to pause

ratio

M =molecular

weight

coefficient

= diffusion
bulk

concentration

Cs=surface

concentration

d = diffusion
p

than

I-t

on pulsatinq
copper

constant

observed

produced

improved.

work

of

higher

is as follows:

Co=

to

shape

were

overpotential,

have

density.

is also

the

where
calculated

compared

they
were

current

copper

[I201

pulsating

as

deposits

bath,
densities

consumption

same

of

et

with

density,

smoother
the

current

Popov

found

er

sulphate

Limiting

layer

= density

ho = initial
An

heiqht

increase

value

of

deposits

thickness

of metal

h,
for

of protrusion
in

r,

which

j.+

pulse

means

sufficiently

to

the

fast

pause

ratio

formation

nucleation

of

in

the

smooth

is given

above

equation

deposits.

The

decreases

porosity

of

the
metal

as,

K8
where

B =
N

time,

Q.

i = current
of

in r

leads

good

achieved.

i = 1
=

quantity

density,

electricity,

hOi3

= integer,

to decreasing

agreement
Also

the

of

electricity

= fraction
K

of

between

in the

these

[122,123,124]

power,

smooth

deposits

on

average

current

densities

that

corresponding

= proportionality

porosity

authors

correspondinq

surface

initially
are

factor.

to

one
to

So,

monolayer

protrusion,
in

this

case

of

metal,

Q = quantity
also

a raise

deposits.

theoretical
found
smooth

less than

expressions

that

substrates
the

and

in electrolytes

limitinq

can

be

diffusion

experiments
with

obtained
current.

good
by

was

throwing
pulse

at

454
Popov
tial

and

in the

Maksimovic

case

2.32

= slope

= exchange

The

of

above

and

current

galvanostat,

during

less

Maksimovic

Cu

range

can

function

minimum
mass

values

transfer

[I51

duplex

give

the

[$I
where

The

from

rates

duty

for

overpoten-

in

bath

current

on

by

simply

state

potentio

close

to

reverse

each

current

reverse

periodic

optimal

have

the

shown

and

to

measured

empirical

of
fre-

overpotential

electrolysis

a semi

range
optimal

corresponds

[I281

pulse

by

the

average

range

Landolt

repetitive

replaced

frequency
that

the

optimum

Datta

and

was

be

periodical

measuring

and

pulse

to

macroprofiles

the

They

potential.

steady

found

than

overpotential

[126].

determined

frequency

model

but

activation
from

are

by pulse

deposition.

single

the

equations

produced

[I271

Cu

respectively.

between

distribution

average

layer

limiting

relationship

t -vs log i plots

sulphate

better

t;p)(l-y)l*5

y
=

are

determined

the

diffusion

pulse

regime.

deposition
of

relation

theoretical

For
be

of

density

the

Dimotrijevic

electrodeposition

quency

the

deposits

to give

and

current

pulse

from

of

was found

pulsed

t*
PP

in the

rough

a Tafel

pulse.

lie,

defines

and

established

using

and amplitude

electrolysis

current

as

Tafel

density

Also

further

deposition

equation

and
other.

[I251

of copper

of

the

limiting
Cu.

equation

Ibls
which

as

-I

+ g

cycle

dimensionless

pulse

period

experimental

values

and

values

derived

from

the

equation

were

in good

transfer

in pulse

agree-

ment.
Chin
of

[I291

copper

mass

transfer

attained
pulse
of the

by
can

pulse

mental

rotating

rates
short

change

generalized
disc

current

theory

electrode.

corresponding

the

disc

to

pulses

of

He
a

high

current-potential

electrodes

plating.
results

Viswanathan
pulse

for

mass

has

current

shown

that

very

of

100-1000

density

frequencies.

Also

relationships

and

his
as

high

A/dm*

results

well

electrolysis
instantaneous
can

indicated

as the

be
that

morphology

deposits.

Rotating
in

presented

on

plating

Models

were
were

widely

proposed

employed
which

to

study

showed

good

the

current

agreement

distribution
with

experi-

[I 301.
et
with

al.

[131-1351

rotating

disc

studied
electrodes

extensively
in ferro

the
and

mass

ferricyanide

transfer

aspects

systems.

Numer-

in

455

ous

solutions

were

A oeneralised

ac

equation

by

based

the

authors

on a diffusion

for

calculatinq

the

inodel

is as follows:

pulse

plating,

mass

transfer

rates.

2.L2

-z

proposed

a,

at
where

c = concentration

of reacting

ions

t = tirne
z = axial

coordinate

D c diffusion
With

appropriate

was

derived

retical

controlled

has

the

for

his

was

at

activation

the

is controlled
can

Puippe

the

Ibl

the

the
tC

= 120

td

where

the

layer

17/i

is

system.

the

duration

be

equal

Cd

inhibiting

presented
on

and

by

time

(td)

in

the

Cd

further

d.c.,

mass

transfer

improved

only

if

concen-

of
of

the

the

deposition

pulse

was

the

general

that

longer

less

a pulsating

reaction

off

diffusion

speed

the

each

[I381

distribution
plating

metal

layer,

the
metal

Ibl

times.

is pulse

if

for

current

uniform
Also

Also

necessarily
high

secondary

deposition.

surface.

however

reported
with

that

electrode

than

distribution

a good

throwing

off

mathematical

times

charging

of

may

a simple

charging

of

pulse

equation

plating

and

discharging

of

the

double

(tc)

be calculated

layer

are
the

in

reasonable
double

and

order

the

to
and

layer.
time

check
within

According

of discharging

as,

to

Pd,

through

was
of

review

metal

[I351

theo-

/ ip

of

Puippe

[I391

caused

authors,

double
=

of

authors

non

transfer
of

electrolysis.

investigators

is in

rate

transport

selected

limitations

to

of

mass

his

mass
results

be achieved.
and

whether
the

by

average

step

of
the

The

any

recesses

concluded

overpotential

same

obtained.

distribution

effect

in

many

studies

d.c.

rate

between

under

and

the

[I371

by

distribution

an

d.c.

power

attempted

current

crests

hence

Shazley

was

from

determining

and

metals.

values

current

the

agreement

electrolysis
that

at

rate

different

all

involving
in

that

be

of

micro

stated

a good

transfer

exceed

that

developed

deposition
in

cannot

reported

for

and

rate

polarisation

will

same

mass

msximum

conditions
[I361

tration

metal

the

ion.

conditions

series,

Fourier

experimental

that

Ogato

of reacting

boundry

using

and

showed

he

coefficient

to
and

If

Ibl

the

of

the

and

seconds

deposit
species

on

in

an

obtained
and

and

(SO4

times
by

study

pulse.

grains

for

lead

to the

current

(pulse

discharge

off

another

anion)

A/cmL

supplied

with

coarser

in

P
and

current

[I401

Au

charge

the

total

and

times

are

negligibly

respectively,
the

then

generator

discussed

the

An

increase

in

Cu

and

Au.

formation

In

density)

and

small

Faradaic
no

damping

morpholoqy

compared

current
will

of deposits

off

time

yielded

the

former

case

of new

irrespective

nucleation

finer

will
occur.
of Cu,
grains

adsorption

centres

of

favouring

456

finer

grains.

bigger

a decrease
on time
of

However

in

grain

does

not

adsorption

pulse

trode

et

deposit

is

smaller

in

of

nucleation

the

potential
The

They

of

and

by

this

-vs

d.c.

the

Also

the

slope

to

decreased

that

of

pulse

d.c.

the

but

on the

inert

on

and

Also

[141].

density,

the

deposition

off

because

deposits

current
of

the

process.

the

with

average

for

that

for

current

same directions

of

coverage

pulse

pulse

crystallisation

deposition

same

curves

the

properties

a certain

deposition
cyclic

that

the

in

was

explained

transfer

and

of
in

at

an

with

inert
the

elec-

quantity

electrode

surface

over

potential

critical
to

of

inert

substrate

smaller

no

of

the

and

clear
of

at

is

intercept

dissociation

complexed

Au

the

the

by

on

method

Honkos

of electro-

resistivity

dependence

of

the

studied

step

of

on

Au/Au1

potentials

potentials,

was

potential

purity

irreversibility

cathodic

to the

size,

deposition

terms

solution

and single

grain

showed

Au

more

transfer

sulphate

voltametry

stress,

terms

mechanism

electron

from

potentiostatically

explained

The

a direct

for

be the Cause

may

increasing

commented

in

during

of

time
with

authors
size

on silver

give

same

using

pulse

was

NHE

charge

study

that

gold

observed

solutions.

the

grain

range

ng off

cadmium

axis.

and Romankiv[l43]

deposited

wide

to

the

nduri
and

Also
the

polarisation

with

kinetics

lysis.

noticed.

the

than

the

copper

phenomenon

found

pulse

line

of

influence

required

as

straight

was

in their

platinum

metal

case

desorption

[I421

of

size

improved

al.

like

in

always

and

plating

Popov

later recrystallisatio

A nd i n the

grains.

of

the

couple

in sulphate

more

positive

than

gold

complex

followed

mechanism

was

Au

frequency

found

O&V
by

to involve

ion.

CONCLUSIONS
The

above

review

clearly

in

plating

of

technique
plating,

amorphous

pulses

in

the

changed
a

clear

the

understanding

a few

near

for
above

still

future

possibilities

of

checking

of

the

use

of

can

metals

of

of

the

expect

pulse

more

of

current.
pulse

research

in pulse

As

papers
from

Pulse

Platinq

for

simple

waves

advantages

were

and

parameters
of

employing

anodising,

plating

pulse

in the

be employed
lines

show

also

process.

wave

by

properties

and

a given

square

on these

produced

expressions

indicated
to

a pulse
composite

mechanical

Theoretical

involved

reverse

further

alloys.

application

as

structures

chemical

pulse

of

such

grained

and

transport

combinations

deriving

fine

mass

advantages

processes

physical,

selection

contains

many more
one

so that

the

various

other

Invariably

many

the

literature

instances

we have

etc.

for

the

and

processes

advantageously

guidelines
of

alloy

above

indicates

metals

pulses

give
Most
with

introduction
and

exploring

in

the
the

plating.

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