Materials Chemistry and Physics, 21

(I 989) l-41

Review

A REVIEW

ON

THE

ELECTROCHEMISTRY

OF TIN

1-A. AMMAR, Department

S. DARWISH, of Chemistry,

M.W. Faculty

KHALIL, of

and

S. EL-TAHER Cairo University, Orman, Giza (Egypt)

Science,

ABSTRACT The 1970. recent In order literature to avoid on the electrochemistry length, only of tin has been reviewed since

unnecessary The review chronologically in each

papers

which

contain

significant manner, the reader are

contributions

are included. arranged

has been written in each section section.

in a bibliographical In this techniques manner, and new

and papers are can follow the

developments

as new regarding

ideas

introduced, ions

and can easily the results future

draw of

conclusions

the

agreement he by the has

and contradictthe liberty of

between

various research,

authors. without

Furthermore, being biased

formulating opinions.

plans for

reviewers

personal

The contents

of this review

have been classified

into

twelve

sections:

(1) (2)
(3) (4) (5) (6) (7) (8) (9) (IO)

Anodic

dissolution

of Sn and tinplate.

Corrosion Passivity Cathodic

of Sn and tinplate. and anodic passivation passivation of Sn, tin alloys, and tinplate.

in dichromate. of Sn and Sn alloys. Sn alloys.

Electrodeposition Electrochemical Semi-conducting Some industrial Cathodic Electron

(electroplating) properties properties aspects

of electroplated of Sn02.

of tinplate.

processes. transfer studies between soluble Sn species.

(I I) Photo-effects.
(12) Miscellaneous Each section studies. is written as concisely as possible, and 190 references are included.

0254-0584/89/$3.50

0 Elsevier Sequoia/Printed in The Netherlands

2 INTRODUCTION The literature rial applications, of basic on the electrochemistry tin plating has attracted electrochemistry. good adherence, solderability, To reach to study the of Sn is extensive. the attention Several uniform of Because many of its industin the in a

researchers are needed

fields

and applied These

requirements and smooth to a large of the

good tinplate. resistance, ability, gations variables, constitution (cd),

include:

deposit,

corrosion lacquering of investi-

brightness,

ductility, power. order

resistance this goal,

staining, number various

and a good throwing has been e.g. of made in

effect

experimental the chemical density steel

the nature organic of the

of the substrate, additives electrolyte, and

the composition the

of the bath,

brightners, Of the

temperature, available

current substrates,

circulation

etc.

various

is one of the most Furthermore, preparation Therefore, large

frequentiy

used because has offered

of its importance easy a on

to the canning for the of

industry.

eiectroplating of it is numerous not

a relatively possessing the work

method

electrolytic properties. a

alloys

of to

Sn find

wide

spectrum

surprising literature which

electroplating of tin.

constituting

proportion

of the

on the electrochemistry has been done on the in a monograph and concise for a scientific with

To cite a large

all the work probably

electrochemistry than of the This the

of

tin

requires review. work by

space,

available

rather survey

in a scientific most important

On the other

band, a comprehensive is most adequate fairly recent and

in the literature considering with the the

review. on in

can be achieved publications detail.

literature such here

emphasis are cited

dealing The

fundamentals,

publications as from ways:

sufficient

literature This arbitrarily viour,

survey is compiled survey can be made according and the and

1970 onwards. (i) in e.g. topic the first method, behaviour, the papers are

in two

classified etc.

to their papers in

topics, in each

anodic are

cathodic to

behatheir

corrosion,

arranged the

according are

scientific

importance,

(ii)

the

second

method,

papers year

presented same topic

chronologically, together. The

compiling second

the papers method of has

which been

appeared chosen

in one it

on the the

because

shows

development of Interest in the

not onIy in the

techniques

research

but The

also in the most

trends

and fields of

of the researchers electrochemistry

as the years pass. of tin are considered

important

topics

research

below.

(I)

ANODIC The anodic

DISSOLUTION behaviour this field

OF Sn AND

TINPLATE solutions represents a good percentage of Sn in 0.1-10 of N

of tin of

in aqueous

the

work

in

electrochemistry. by Awad

Anodic [I].

dissolution

NaOH ments which

solutions

was studied

and Kassab

Based on polarization

measure-

and the calculated excluded

values for the electron number, a mechanism was proposed 4+ the dissolution of Sn as Sn at low current densities (cds.). However, rate of oxide film formation exceeded that of dissolution, where-

at higher

cds the

upon an and 02 The study

appreciable

rise

in

potential

was

observed,

the

electrode

became

passive,

was evolved on the passive film. potentiodynamic the anodic technique was used by Golubev % Sn in and solutions Kadyrov of [2] to

and cathodic 0.1

processes

on 99.95

NaOH/NaCI and an the

mixtures, formation peak. this

and in pure of SnO; anodic the

M NaCI. being

Anodic

processes with

included: the

dissolution of Thus, of Two

latter

associated

occurrence ratio.

anodic

The ratio

behaviour of pH

was affected >

by the in the

OH-:CI-

increasing anodic also

in solutions

1I resulted
oxidation curves,

appearance

a second peaks

peak which detected

was attributed

to the polarization

of SnO to Sn02. and these were

were

in the cathodic

attributed

to the reduct-

ion of SnO and SnCI2. The potentiostatic zation of Sn anodes of method was used by Dohi plating above it of of the and Masaki An [3] to study film was The was of to the polarion was to in

in H2S04/SnS04 at and but

baths.

oxide

formed film lowered H2S04

the surface stable the

Sn anodes V

passivating when the the

potential. potential

up to -0.4

(vs SCE),

dissolved Sn. the

spontaneous and the

electrode impurity

potential content

Both anode

concentration were found

solution

material

influence

the results. The electrochemical by Brainina of behaviour et al. [4] of Sn in HCI solutions with was studied by inverse system. positive,

voltammetry

using an oscillograph

a two electrode various

Electrodissolution neutral

Sn from complex

electrodeposited ions. of

electrodes

produced

and negative of the

Results

anodic [5].

dissolution The

Sn in acid valence nature had an of

chloride the

solutions

were

reported from and

by Johnson and Liu 0.4 the to cd. 2.4, and was

apparent

dissolving of

ions

varied

Complexing was SnCI;. electrochemical

a function of the 2+ of Sn with Cl-

and

concentration effect,

electrolyte the

important

and

dominant

product The

dissolution

of

Sn

in

HCI

solutions Theoretical

was

investigated of the

using results by the

polarization was given. a chemical evaluation

measurements The first step The

by Yarunina

et al. [6].

analysis

was electrochemical dissolution current

in nature, was

and this and

was this

followed enabled

reaction. of the rate

calculated,

constant

of the chemical and rotating the active

reaction. disk techniques dissolution diffusion 2. The of tin were carried out by

Measurements Stirrup

using impedance [7] to study was

and Hampson Tafel

in alkaline were

solutions.

The anodic The reaction

slope with

57 mV/decade to OH-

after was

effects results to form of two Sn in Tafel The

eliminated. a quasi-

order

respect followed

indicated HSnO; acid slopes authors

reversible The solutions

charge same

transfer

by a chemical the [7]. more anodic They cathodic

reaction

.
perchlorate of 85 and

authors

[EI] studied techniques being at

dissolution observed

using the same the latter

41 mV/decade;

potentials.

concluded

that

the

dissolution stages

reaction

consisted rates.

of The

two rotating active

consecutive

single-electron

charge

transfer the same

of comparable [9] to

disk technique dissolution of

was also used by acid chloride

authors The of

study the anodic for The dissolution order to of

Sn in after

solutions. the effect The

Tafel

slope

was 64 2 reaction

5 mV/decade

eliminating to Clions. and

dissolution. current mechanism was

was one with hydrogen transfer. ion

respect

measured

found

depend

on the

concentration,

the proposed Anodic tiostatic order with

involved quasireversible solutions [IO].

charge was The On the

dissolution method respect by

of Sn in alkaline Costa and were to fit Cullere

also investigated Tafel slope and

by the the

potenreaction a

to OH-

determined. the results. the

basis of

kinetic

parameters,

mechanism Lyungrin dissolution technique

was suggested and Pnev [I of Sn from

I] measured

anodic

polarization

curves for the

using the

electro-

the surface

of a glassy C electrode

potentiodynamic

in HCl solutions. and ionization reactions over a wide of of Sn were of studied in HC104 solutions by

Discharge Slutskii the rity

et al. [ 121 on Hg

range

Sn concentration polarization the data

in solution and

and in

amalgam

using a combination Based were

radiochemical, of

electrocapillaregions showing curves. electrode the was

measurements. portions

on the combinatjon anodic

obtained,

two Tafel The ware effect kinetic

observed in the for the

and the

cathodic

polarization

parameters

discharge-ionization An

of Sn on an amalgam was proposed and

determined of

by Slutskii,

et al. 1131. in the amalgam

equation and in

to describe equation

Sn concentration

solution,

this

based on the experimental The ted by effect of

polarization on the [14] in

curves. discharge HCI04 and ionization on tin of Sn was investiga-

temperature and Krol was

Bukhman of

solutions the

amalgam of the

electrodes. cathodic of and the

Increase anodic reaction

temperature without

found

to decrease the transfer

overvoltage

processes studied.

changing

coefficient

or the

mechanism of Sn were

The same reactions et al. [IS]

of discharge amalgam

and ionization electrodes curves.

studied by

by Gorodetskii analysis

on stationary

in HC104 The diffusion

solutions

of the transition

zones in the determined. the

polarization

parameters

and the exchange Costa in MeOH ted NaBr the et af.

cds were f16]

studied

anodic

dissolution mV/sec the

of

pure

Sn in The

0.1-1.0 authors

NaBr

by cyclic formation

voltammetry of SnBr2

at 50-1000 followed by

scan rates. of a

suggesand

addition

solvent

molecule

to give NaSnBr3.MeOH. and Lotfi of [17] Sn in under A used rotating disk and impedance M of measurements The was as to Tafel 3 with

Dickinson study the

dissolution

alkaline all

solutions

(0.1-2.0 order

NaOH). reaction Sn(OH)2 [IS]

slope was 30 mv~decade respect to OHon ions. the

conditions~

and the

mechanism was

involving proposed.

Sn(OH) The

and

adsorbed performed

intermediates

electrode

same

authors

E.M.F. resulting the

measurements from

in

order

to

eiucidate

the

nature

of

stannite The

ionic

species proposed potential. by the

the anodic

dissolution Sn(OH);, of Sn in

of Sn in NaDH and calcuiated phosphate the

solutions.

authors

formation The

of the species behaviour [ 191.

its standard of pH 6.7

electrode was

oxidation and Tissot

buffer

examined with The

Do.Duc passivity reaction soiubie reactions rotating cathodic species ring-disk

Although

investigation with

was mainly anodic

concerned

of Sn, the paper was species of disk

deals to a less extent and

dissolution. by

anodic of

diffusion-controlled, from the solution.

passivation

was [ZO]

started

precipitation the

The same authors solutions During ring in the the

investigated before reaction the high

dissolution using disk, a

Sn in neutral and ring-disk

phosphate electrodes. on the low to

region anodic from 0 of at an

passivation on the of

current produced current

was observed on the was

resuiting and

reduction potential.

soluble The low They ring-disk

disk at

potential the

attributed

formation

insoluble by the first

product. rotating

also investigated technjque passivation. of S&I) [2 1I.

the dissolution Soiuble

of Sn in alkaline were that, produced during

phosphate in the the

Sn species

and second stage,

stages

of

Evidence

was also given

second

a smali

amount

species

was formed, [22] They the anodic

and was quickly investigated observed alloy that .the

oxidized anodjc

to Sn(IV). dissolution of Sn by electroeffect, (and some

Popescu chemical

and Radovici

polarization. that The

alloying

Sn with

Cu had a marked the least

in such a manner ~~rrosion) polar rate.

containing

27 % Sn gave anodic [23],

dissolution of Sn in

behaviour,

including et

dissolution,

solvents

was reported of acid the were into

by Kostromin dissolution studied and

Characteristics in hydrochloric of the rate the the study anodic

electrochemical and Buzlko components an

features 1261,

of

Zn-Sn

alfoys

by Titova of the

In the alloys was the

determination in HCI, and in

of transfer of their

solution

of Zn/Sn increase of

electrochemical of the

characteristics, base. The

established metal

effectiveness additive

metai were

behaviours

base and

the metal Anodic and Zhilina

in the alloys of Using Sn in a

found to obey different perchlorate at solutions

rules, was studied by the Gusev authors

dissolution [El, that

sodium

kinetic containing low

method

different moI/L

temperatures, anodic

established of Sn was

in solutions at

O.IYOl-0.1 poiarization

of NaCIOlt, to

dissolution polarization, dominant. to acceiedissolution

limited at

relatively high

potentials

chemical was

However, Increase rate the

relatively

potentials,

concentration

polarization

in both anodic

temperature dissoiution of

and the concentration Sn The activation

of NaC104 energy for

was found the anodic

was determined. Wu and Hao oscillations were in [26] the studied the anodic of of behaviour Sn in NaOH, and the accompanying These potential osciliations cd,

anodic

dissolution

NaOH the

solutions. temperature

influenced

by the

concentration

of electrolyte,

convection, attributed Sn(OH)4

and by the to the

presence

of stannite between anodic

or stannate formation

species.

The

results dissolution

were of

competition

and chemical

(II)

CORROSION A bibliography

OF Sn AND TINPLATE on the corrosion Factors [28]. additives studied by Board of tinpfate affecting was the given by Collins of [ZT] in a review aerosol of cans tinned [29]. were steel The canning the

containing discussed for food

256 references. by AnagnostoFoulos cans by various was food

corrosion of the reviewed

The inhibition coatings was

corrosion by

Massini

corrosion of some corrosion

of tinplate sorts of

at subzero and Steele lacquered

temperatures [Xi].

in relation

to the

Karakasides in relation

[ 311 reviewed to the

of tinplated of food. of

food cans both

and plain

composi-

tion and type Corrosion [32] Unless in HCI,

Sn was

studied and

by the H3PO4

thermometric acid was on the to retard solutions present, dissolution

method of

by

Baraka

et

al.

HN03,

H2SO4 cathodic

various

concentrations. only in HN03

O2 or another The effect The

depolarizer anions found

Sn dissolved

and HCI. also so:studied.

of various anions were

of Sn in 4 M HNO3 was in the order H2POi >

dissolution

> HSO; Gouda et

> Ct- > NO;. al, [33] investigated oxalic, tartaric the corrosion and citric behaviour acids) corrosion of Sn in organic 2-6. to acid With more

solutions increasing negative shifted process lexation oxalate buted

( 10V5 to 10-l acid values, to more concent and the noble

in the potentiat

pH range shifted

rat ion at corrosion values, and

pH < 4, the rate the increased. corrosion control,

At pH 5-6, rate and this

the corrosion At

potential the

decreased. was explained

pH 2-4, by the in the

of corrosion

was under

anodic

comporder:

of Sn2+ by the acid anions. > citrate to film > tartrate.

The complexing of corrosion

ability

decreased

Inhibition

at higher

pH values Sn

was attri-

formation et

as a result reported

of hydrolysis a study

of the complexed corrosion media. Fe-Sn, media

2+ .
of iron-tin, of the was

Paramonov, iron-chromium corrosion conducted

al. [34]

on the

behaviour

and tin-chromium of low

pairs

in models couples developed

of food of Fe-Cr,

The study and were

behaviour with

short-circuited the current internal

Sn-Cr

by measuring

in them The

using

a speciaIfy

constructed 3 % NaCl couple, solutThe

microammeter and 3 % HOAc characterized ions were Some aspects

resistance. the

corrosion

solutions. of the

In 3 % NaCI, corrosion et kinetics was

most

electro&hemically couple. of tin cell

active in NaOH method. with

by the highest reported

current, al. [35]

was the steel-Cr of corrosion using the A three polarization

and mechanism

by Thangavel

potentiostatic electrode curves. Under

Sn was 99.99

% and NaOH

1 and 3 N,

a low IR

drop was used to measure conditions, the corrosion

the potentiostatic of Sn was governed

steady-state

by the rate-determining

step:

Sn

ZOH- --t Sn(OH)2 rate-determining

2e (for step: (for the

the

anodic

reaction)

and by the Na+ +

e + Sn + Na(Sn)

cathodic

reaction),

Couda, nant ions these were acid to

et al.

[36]

studied

the

corrosion citric and and function oxalic M oxalic The

behaviour tartaric the of acids

of

Sn-steel at pH

couple 2-6. The

in

stagvariatin values

deaerated of both

solutions the

of oxalic,

acids

open-circuit followed 0.1 M citric as in to

potential as a and -3

galvanic time at

current until the and

of

the

couple state M

solutions reached. at pH 2-4,

were In

steady in 0.1

pH at

2-5, pH

tartaric found was of 2 the

as well with both

IO

acid

2 and in

3, steel these and

was

be cathodic by of

rspect the

Sn.

corrosion of M the

behaviour acid

solutions the acids kinetics at

determined inhibition

complexing reaction.

strength In 1O-3

anion and more

the

cathodic

citric the

tartaric noble

pH of

and 3, as well couple. In of with steel tion low3 these This

as at pH 4 in tartaric result was attributed and as in tartaric 0.1

acid, to the acids

Sn was weak at

electrode

complexation pH acid 5 and at pH

M citric, acids, to the

oxalic as well steel. anode

of Sn in these solutions. -I 6, and in 10 M solutions 5, Sn was after initially some to film anodic time and

M tartaric reversal of

respect became on the The

However, of the

polarity behaviour

occurred was

couple. immersed multiunit Paramonov containers was the of the

The

attributed

forma-

Sn electrode

when of by

in these

colutions. canning The containers authors showed in a that 3 % the

corrosion was

behaviour studied

(tinplated) et al. was of [37]. a

NaCl

solution of the

assembly each of

multiunit component cell. by the and

canning parts

complex

electrochemical or, such in the simplest was

system, case, deter-

composed corrosion

a multiple of

a Z-electrode mined lytic loping both tinplate, on the of

In general, operation also by the

behaviour of

a system sheet (Cr-Fe,

macro-couple of the

Cr-plated

steel-electroSn-Fe) the deve-

operation of the

micro-couples electrodes. potential, development for 24 hours.

surface the

of each

indicated the

In studying the of

corrosion current, corrosion, substrate

behaviour and were the

galvanic rate,

couples, which

corrosion the

corrosion contact The steel

corrosion in

characterized at

measured both

3 % NaCl

solution

IS-20C

was anodic The

to Sn and to Cr electroplates. of Sb on the Jr. corrosion et al. of [38]. Sn in deaerated role were played prepared 0.33 by by data. A mechanism were acid found greatly M citric acid was

effect by

investigated the and rates sed the in corrosion the

Leidheiser Sn was rates related amounts

The alloys from

Sb in

accelerating

of

studied. were

Sn-Sb determined

electrodeposition, The corrosion propocatalyze accelerated

corrosion linearly small

polarization alloy.

were

to the of

Sb content

in the

was to

which

Sb oxide

on a Sn substrate to deaerated citric

H2 evolution

reaction.

Addition

of NO;

8 the corrosion of NO; ion with rate of unalloyed Sn. A relation rate. was proposed to describe the effect

concentration the corrosion

on the corrosion rate were

The results to

of NO;

and Sb in connectsurface on Sn by Baraka Br-, I-, which

attributed

a partially

oxidized reaction

could serve as a very The open-circuit et al. [39f. Gq, tant the so:-, The ClO;,

effective potential

catalyst

for the H2 evolution salt solutions

of Sn in various of the Sn eiectrode

was measured solutions

potential EMI;, In

in aerated

of Cf-,

IO;, all

H2POi, solutions, (immediate

(steady-state). directiy measured oxide film of

and Cr 02-was measured unt i I Crow-, 2 7 the steady-state potentials were higher measurements), to Impart potentials The first of passivity with the indicating to the that metal. the

ccmsthan pre-

values was the into In

immersion ing to the studied W2POi shift

not sufficient steady-state two groups.

Accordthe anions SO:-, in a

change

concentration, included Cl-,

were and

ciassified ClO;

group anion The

HS0& resulted

this

group,

increase

concentration opposite

of potentials for

towards

more group

negative which

values.

behaviour Br-,

was found BrO; and on was

to occur II anions.

the second

included

IO;,

CrOi-,

Cr&,

The effect

of the effect

latter

anions

on the anions

corrosion on the

of Sn was explained of O2 which

the basis of a paraltel the major cathodic

of the same &omp~ementing

reduction

reaction

the anodic by House

partial and

reaction Keisall

(corrosion). for not ClSn/HqO consion of the the

Potential-pH system dered EH-pH results at in

diagrams including

were

constructed

[40] species of

298 K, the

mononuclear diagrams. solubilities

and polynuclear In was addition, described.

hydroxy the

original and

Pourbaix %-oxide

effect The

diagrams

significance

to Sn corrosion

and hydrometallurgy

was discussed.

(III} ihe

PASSIWTY polarization

AND

ANODiC

PASSIVATI~N

OF

Sn, TIN

ALLOYS

AND

TINPLATE potenof

of massive and electrodeposited [41] of in +3 V

Sn electrodes from peaks an at

was studied initial -0.72

tiodynamically -2V to a vertex

by Anwar potential the

1 M Na2C03
(2 SCE). The potentials the current

solution current

potential and -0.52V

corresponded respectively. remained The

to At

equilibrium 1.08 V,

of

Sn/Sn(OH)2

and
to 2.28

Sn(OH~2/Sn(OH)1

about

increased

sharply of

1 mA/cm
V of passive was Sn in

and

constant,

giving a current this layer current to Sn02

plateau, plateau The

until to

a potential the direct products found film,

reached the

author

attributed

oxidation on the

pores of the Sn(OHf4 were examined

anodic

electrode Cl2 stages

by electron media

microscopy, took place

and ware on the Sn02

to correspond formed

to Sn02. later

evolution

in alkaline

in the

of oxidation. Anodic Ichikawa polarization f42f. This Cast of afloy electrodeposited showed a distinct exhibit at Sn-Co attoy was studied by Tsuji and

active-Passive the 4OOC passive caused

transition behaviour the

in 5 % H2S04 Aging to

and 5 % HCI04. of electrodeposited

alloys in

did not argon

markedly.

alloy

gas

anodic

polarization

become the

similar

to that film on

of the

the

cast

alloy. of the

Reflection

electron

diffraction alloys This

studies of diffuse

protective typical resulted

surface

ele~trodeposited materials.

showed poorly

patterns material

of amorphous

or poorly

crystalline

crystalline

in good corrosion were NiSn, made

protection by Clarke

of the alloy. and Elbourne [43] on some intermetallic compounds of these

Passivation compounds showed

studies

of Sn like over

CoSn, FeSn2, range than of

Cu3Sn, Cu6Sn5 PH. of The their

and SbSn.

These

passivity were

a wide

passivation elements. by further for

potentials This was

compounds to the

markedly

lower

those was

attributed to higher use of

rapid

film

formation The

which of

followed

oxidation the

oxidation these

states.

importance

establishing

passivity

technical

compounds [44]

was discussed. reported some recent data of on the tinplate material passivation through films. the The Sn of by

Aubrun layer

on the

tinplate

produced

passivation mixed oxides

formation denoted

an oxide sno
X

coating

of SnO and SnD2 of these

with were

a new analyzed

phase

tentatively

The

compositions were

by electrochemical of The the tin layer

methods. occurred were

Similar through formed then

studies reaction

carried air

out for Cr plating. or by anodic

Oxidation

with

electrolysis. the

different SnO was

oxides first

at different and

potentials. and by the

This,

by raising was

potential

formed, was to of

SnO

Sn02,

finally tin

SnOx layer. of

produced. tinplate found

Corrosion did not

protection contribute adherence

provided corrosion

exclusively protection.

Cr-piated SnOx was

The

presence

to destroy

the

phenolic-epoxy

lacquers. [45] observed in all two 0.01 different to 2.0 oxidation N NaOH patterns at 25C. by the The galvanostatic first pattern

Shams El Din technique described NaOH, cteristic region before showed with fit the the for tin

amalgams of

the behaviour

amalgams

of varying

concentrations The first second oxidation

in 0.01 pattern pattern

and 0.1 N was charashowed a

and of concentrated of dilute associated 02

amalgams in 2N

in 2N NaOH. NaOH. of The

Sn amalgams with the The

formation oxidation

SnfOH) of and

evolution. of

curves

film on the electrode surface 2 dilute Sn amalgams in 2N NaOH a region relation: A and atom for an arrest associated log i to The ele-

a region formation results (t

oscillations of HgO.

in potential, The author i

found

the

log t = A-n

= time was

of passivation, governed by the

= current, of metal

n = constants). diffusion to film the

passivation ctrode

process

rate

surface,

and by the physical

and chemical

properties

of the oxide

formed

at the interface, Petrov current 25-30 and Bizheva [46] reported of on the passivation The g/L. bath of Sn by 50 was Hz alternating of: Na2C03 good

in an alkaline and rongalite films 5-30

solution

rongalite. 3-5 at

composed black,

(CH2(0H)S02Na) were min. formed The

Uniform,

compact,

adhesive of

passive after

a cd of 62.5-100 of the

A/dm*, film

and a was

temperature ~-5.5 u as

l8-20C

thickness

passive

10

determined

by the weight

increase tests. of Sn

method.

The

passivated

Sn plate

samples

showed

good resistance The stannate mic anodic

to corrosion behaviour

during

delectro-deposition and Sripatr [47]

in

alkaline

Na

and

electrolytes

was examined of Al

by Gabe found

using the Sn giving to

potentiodynaan increase the activa-

technique.

Addition

was

to depassivate were

the found

in the anodic tion energy A new

cd of 4 to 20 times.

Such additions

lower

of the dissolution passivation

process. was described by Jargon A and Maschke [48] for

technique resistance oxide

improving bed which the heat

the corrosion alIowed of Cr-Cr the

of electrolytic

tinplate.

technique without high

was descriincreasing and

coatings

to be applied resultant

to tinplate had

temperature resistance. of by

electrolyte.

The

product

corrosion

Passivation Hampson rotation Primary the only to [49] speed,

Sn the

anodes

in

NaOH

solutions The the

was

investigated of

by

Stirrup sweep

and rate,

voltammetric of

method. NaOH by and

effects potential

varying

concentration was initiated

limits

were

studied. involving not Sn film for

passivation of the

a dissolution-precipitation species. species, positive A but Secondary also the

mechanism passivation direct

blocking the Sn(IV)

electrode of S&II)

by Sn(I1) to Sn(IV) At more

involved of

oxidation soluble in a more current

oxidation of the

species. efficient

potentials, possible

dehydration was

resulted

passivation.

explanation

proposed

the observed Anodic ned by

oscillations. of tin in buffered tiampson [50] phosphate a variety electrolyte of (pH = 3.1) A was examinumber of

passivation and

Stirrup processes

using

techniques.

anodic

occurred On started slope

depending anodic to for

on potential polarization, anodic was

and the conditions the electrode to

at the electrode/ filmed with

electrolyte a phosphate

interface. layer Tafel

originally form V/decade three

undergo this

dissolution about

Sn(H2P04.HP04) as calculated consecutive electrode was

species. from

The

process At

0.046

impedance

measurements. occurred.

more first

positive

potentials, blocking The

passivating by the The

processes by

The

process

involved

of the

Sn3(P04)2 formation second

a dissolution/precipitation by also The a slow involved third

mechanism.

second and for

process

of SnO process

three-dimensional a paralfel

nucleation path the

growth

process. of

reaction of

the

formation

soluble species.

Sn(I1) species. The relative

process of SnO

consisted and Sn02

oxidation on the

of Sn to Sn(IV) electrode were

quantities

formed

dependent In an

on the experimental investigation alloy the on the

conditions. electrochemical acids behaviour of electrodeposited Abdelaal determined densities. et al. 80 $

tin-copper measured slopes, the

in some cathodic

carboxylic and anodic

and buffer

soIutions, and

[51] Tafel

polarization the

curves,

the The

transfer curves

coefficients, reveal two

and

exchange arrest

current potentials

anodic to the

polarization

successive

corresponding

11 systems: The of SnO~/SnO or SnO~/Sn(OH)~, measurements corrosion of and Cu20/Cu on the the before circuit the O2 evolution took place.

paper pH, and

also contained data for the

open in

potential

as a function studied (acetic,

alloy

solutions

citric,

and tartaric [52] wrote

acids). a review on the nature and &omposition e.g. of in of the surface films

Gabe (including

mixed

oxides)

produced reactions,

by various and staining. after

processes, Results polarization the

atmospheric X-ray NaOH

corrosion,

passivation, spectroscopic

tarnishing studies et in al. the of

photoelectron solutions were oxide and

tin

electrodes The results region.

given by Ansell and hydroxide were

[53].

indicated At

formation potentials,

of stannous stannic over A. the oxide

pre-passive

higher

hydroxide range -0.95

formed.

The thickness

of the Iayer

was evaluated 30-86

potential

to +0.40 passivation

V, and was found to lie in the range of tin in sodium hydroxide solutions method. according

Anodic lescu until quent blocked Once

was investigated The to the of authors Tafel the the

by Barbushowed that

and Popescu Sn(O~)4 was

[54]

using the the on

potentiostatic dissolved

formed, of OH

metal the

law. metal Tafei covered

Subsesurface law. with and in

adsorption these the Flade OH. on the

active

dissolution

centers

centers,

and

anodic was

dissolution the

no longer entire

followed

potential This was

attained, by the was

surface of a thin

became film of

adsorbed Sn(OH)4

followed

formation faster in

Sn(OH)2 than

anode.

Passivation

diiute

NaOH

solutions

concentrated Radovici of Sn in

ones.

Increase

of temperature studied on the

inhibited of Clthe

the attainment ions on the theory Clions

of passivity. anodic of on behaviour and and

and Popescu [55] alkaline of solutions

the effect basis of The basis

kinetic of

inhibition passivity in

passivation anodic

electrochemjca~ was discussed ions. [56]

reactions. on the

rofe of the

dissolution

activation

energy

presence

and absence The same

of these authors

measured of curve, of Br-.

the Br-

anodic ions at

polarization different

on Sn in temperatures.

0-I N

NaOH In the Tafel

containing active

various the

concentrations polarization

zone of

metal Once

dissolution the anodic

occurred

following criticai to the Tafel law

the

law in presence was attained, of Sn(OH)2

and absence

dissolution and led the

potential formation was no

adsorption and

of OHthe

stopped final

anodic

dissolution, film -

Sn(OH)4Increase

protective

and

longer

applicable.

of Brfilm

concentration and produced related in acetic, to

and increase an activation and

of temperature effect. corrosion acids were as well oxide a

lowered

the stability

of the passivating

Electrochemical

measurements alloy

passivity tartaric

carried as in films pH

out on 80 % tin - 28 % zinc buffered were range. solutions when of various the alloy

and citric et al. [57].

pH values was

by Abdeiaal, in

Stable over

formed

immersed

buffer

solutions corrosion

wide

The paper

also included

some

investigations

on the

and the

corro-

sion potentials

of the alloy

in the solutions

investigated.

12 Popescu SnjZn alloy and Radovici in NaOH The alloys to corrosion [58] studied the passivation and anodic d~ssoiution of the

and H2S04 which had

solutions the

by gaivanostatic best

and p~te~tiostatic and hence $

measuthe Zn best and

rements. resistance

showed the

passive behaviour, 75

following

compositions:

% Sn + 25

87.5 % Sn + 12.5 % Zn, The acids buffer eIe~trochemica~ behaviour et al, of 80 % Sn-20 Upon % Zn alloy in some carboxytic

was reported solutions film

by Issa

f~9]. the

immersion

in aerated formed

and deaerated a thin protecof on SnO2 by the the the or fssa 80 %

(pi-i = 0.8 to 12.2) which was stable

~lectrodeposited a wide pH range. some to

alloy

tive oxide alloy aIloy

over

Anodic kind the of

~ulari~ation oxide film of

in acetic, surface.

tartaric

and citric the

acids

produced current

Increase in
to 02

anodic

led

formation were

Sff~~H~4~ et al.

and then

evolution 80 $

Simifar Sn-20 formed

measurements 6 Pb alloy. a thin protective of

reported to film alloy

[ELI] on e~e~t~#~epos~ted [59], 1.4 to before al, [Sl]

SimiIar oxide Sn/Pb

Sn/ZO % Zn alloy salutions of pH

the Sn/Pb alloy 11.68. Also,

in buffer produced

anodic

polarization

the

SnO2 or Sn(OHj4 Mamedov of SnTe-Ai~I~I~ and pitting that the aiioyinq passive that et

O2 evofution. used the in 0.5 occur potentjody~amic N N&L The technique alloys kept ta study their the initiaf It behaviour passivity was found cd in

solid solutions did not with an

corrosion of SnTe state the and anodic

even

during caused of the of

anodic an

polar~~a~~#n. increase in the

Ga

or Ga2Tej

anodic It was

intensification

cathodic these

processes. alloys was

also upon

shown

and cathodic formed.

behaviour

dependent

the type

of solid solution

Electrochemical passivity Kraitsberg pyrolysis reported of Sn, i,e. f62f of

measurements an SnO2 the in

were Thus,

also made the

on the of

final

product

of

the

anodic used by by

impedance of to film a

a Sn electrode of Sn02 plate.

was

to measure vapour

parameters applied

electrodes quartz

(obtained The

SnCf4

air]

polished

author

the poiarizat~o~

curves of the SnC$ electrode of the anodic behaviour by Do

in 2 M Na2S04 and passivity Tissot of [19] tin in using The neutral cyclic anodic of

A ~omprehensiva phosphate buffer (pH

study

= 6.7)

was reported and

BJC

and

vaitammetric, reaction solubfe Detailed was

potentiostatic

galvanostatic and passivation and film the

p&se

measurements, effested at more by

diffusion-cantrofted, followed on the

was
growth film

precipitation pot&tiai% passive

species, studies

by nucleation composition of

positive the

anode

showed

that

film

was composed

of Sn hydroxide passivation and

and phosphate. alkaline using solutions the (0.2 M borate buffer) potentioa of Iarge this under

The anodic was studied static amount charge and of

of tin in slightly Harkerman [63], The during

by Kapusta gatvanostatic charge was in

potenti~dynami~~ that onfy a although fraction

techniques. consumed film

authors anodic initial

observed

oxidation, staqes

was consumed

growth.

The

of metai

passivat~on

dynamic Two

conditions

were

best were

described suggested For

by Muellers to describe below

dissolution/pr~~ipitation the kinetics (E af SE), At film

model. formation

different

equations

under potentiostatic dependence the growth in the light Vertes same light was rate

conditions.

potentials the

1.6 V

a logarithmic potentials discussed

found

to hold between

charge

and time. The

higher were

was co~trolied

by a nucleation growth. Moessbauer electroplates,

process.

results

of the theories et al. [SS]

of film the of

used

emission

spectra the used

in

order

to of

throw some

on the

cumposition in such the in the

particularly authors

presence the same the of

metallic in order

constituents to study

electroplates. films. farmed

The

technique of

passivating passive

Measurements on tin. The

revealed thickness

presence this

Sn(IV) film

compound (0.8

film

passive

to 2.5 nm) was a function and Polaczek [65] used

of the applied the X-ray

potential, technique content by of in the order to

Feret estimate ion films

fluorescence

the thickness on tinplate. the

of the tin coating Using an X-ray

and the chromium spectrometer for tin

passivatthe

aided rapid coating

a computer,

authors of the

described weight

experimental the

arrangement of the

laboratory and the

measurements Cr content of

(and film

hence

thickness)

the passivating to of Sn coating thickness

on tinplate. was

The iron K 03 intensity, measured relation and calibrated

which against the

was inversely destructive chromium by the K tin

related methods 03 line coating

thickness, measurement.

The

observed layer

between

intensity thickness. X-ray passivated passive

and the weight

of Cr in the relation

surface

was affected was suggested, and by

A matham~t~~al photoelectron electrolytic farmed solution results

for this effect measurements were

spectroscopic tinplate on tinplate

electrochemical Azzerri treatment et al. and

analysis

of The

surfaces

made

[661.
by

layer

by cathodic by means with

dichromate of XPS

dipping analysis. and

in dichromate Electrochemical flow discharge

was examined were

and electrochemical absorption in relation depth

compared data,

atomic

spectroscopy to the

spectroscopy

and were

discussed layer. XPS

solid-state obtained

properties far

of the compounds purposes. al. [67]

in the passive

profiles

were

quantitative Ammar et

reported of Cl-,

on the Br-

~Iectrochemical ions.

polarization of at

and Sn was

passlvati~n studied in

of Sn in neutral 0.1 M KBr, KCI,

solutions and KI

and I-

Passivation technique in the

using the was

potentiodynamic first scanned The the three

various direction

scan rates. and was was

~OtentIodynamic reversed 4V. to a

poI~r~~~tion final curves cathodic were

anodic

potential. given for

highest

anodic

potential different for

reached

Scanning

solutions etc. An

under

conditions the results halogenpassivating

aerated, deaerated different Stan -i.e. was given on the basis of the formation containing potentials compounds in the passive data

rates,

explanation

of Sn oxides, as deduced

hydroxides,

and other the

layer,

by comparing

to the thermodynamic

for the formation

of these species.

14 Ammar sulphate solutions Only solution one et al. [68] reported of on the anodic behaviour studied the In 0.1 and in passivity aerated, of Sn in

solutions. of

Passivation and

spec-pure alone all

Sn was using results. volume) solutions,

unstirred technique. and in the

H2S04/Na2S04 peak was

Na2S04 in

potentiodynamic 0.1 M H2S04 the

anodic

observed and

containing during tin solution. in for

75 % acid anodic surface The the the cd The mV/sec

25 % (by In all

M Na2S04,

Sn surface film develowas sulData Tafel acid in of and were

was etched ped on the in

polarization. during thickness anodic of

a grayish and a film thin white

white

polarization, the grayish and was

precipitate on acid. anodic cd for the

formed phate were slopes, sulphate the

white very the

depended in pure and peak 0.1

content compiled the

acid/salt corrosion (Icor), effect

mixtures, potential the of

(Ecor), peak was I-50

cathodic and in

corrosion

passivating scan rate and possible limitations

potential

solutions. I-100

demonstrated mV/sec of (stirred SnO,

M Na2S04 Use

ranges

(unstirred), the The was

solutions). Sn02,

thermodynamic Sn(OH)4 discussed. based sulphate ion was in the Film

data anode

indicated film.

formation of by a the

Sn(OH12, treatment

thermodynamic

formation kinetics. passive up to

governed

dissolution/precipitation the possible

mechanism occurrence of

on diffusion anions not film

Kinetic film, 2.5 V,

evidence mixed with

indicated the the oxide poor

in the

and hydroxides. electron

O2 evolutof the

detected whose

indicating were

conductance

passive

formation

and growth

mainly studies

caused on by

by ionic tin

conductance. in concentrated et scan sweep observed equilibria the al. [69]

Triangular sodium in oder two single potential forward ions. nature

potential solutions the

sweep (I-10

voltammetric N) of were

pure

hydroxide to study

carried

out

Muralidharan The At forward faster were

passivity

Sn in -1.12 in

these to -0.9

solutions. V (SCE).

revealed rates, in in a the the

separate peak

peaks appeared.

in the

region

Oscillations of

the

potential/cd or

curves

regions

characteristic of SnOg-

Sn/Sn(OH)2 concentration by

Sn(OH),/Sn(OH), found to to first

scan. Increase Such of the oscillations passive

was the

increase the

oscillat-

were oxide film.

attributed The

authors of that the

non-stoichiometric peak potential model was

dependence revealed

anodic

and peak most

current

density

on sweep

rates

a pore

resistance

probable. and Da Silva oxides these the in [70] reported sulphate on the solutions. in cathodic showing galvanostatic The formation and reductand with reductSn(II)

DAlkaine ion of tin/tin of of

sodium were

galvanostatic Na2S04 currents. of

formation solutions Two

reduction variations ion

oxides

performed and the thus

oxygenated reduction the of existence the film

anodic

formation observed, results, of

transition film. anodic

times Using

were these

S&V)

and

in the The solutions

the

composition studied

was deduced. molybdate in modifying on and tungstate the the anodic basis

passivation

Sn was [71].

in chromate, of these anions were

by Bijimi curve anions

and Gabe of were Sn was likely

The role and

polarization that these

reported,

the

results anodic

explained

to participate

in the

process.

Potentiostatic by DAlkaine under and

growth Da

of passivating Silva [72].

films

on tin were

in

Na2S04 made the by

solutions changing by (1 was M

was the

studied growing

Experiments and

potential reduction slightly

potentiostatic The

conditions, reference M

analyzing was 0.5 and M

film

a gaivanostatic Na2S04). used. A The which

technique. alkaline solution showed distinct

electrode NaOH in

Hg/HgS04 Na2S04)

(0.001 three

also

voltammograms were specially

anodic

peaks

three The

cathodic mechanism

processes, of

in slightly

alkaline

solutions.

passivatian

was discussed. The influence of sodium hydroxide and Sn concentration DAlkaine carried [73]. out in on the A primary of the passivating growth of film the of with only the their

on Sn was described primary passivating

by Biaggio film at only on various the

study

was OH-

slightly As the

alkaline film was Sn(II) peak

solutions formed was the

1.0 M NaC104/NaOH hydrogen oxidation peak evolution, state of and of

concentrations. peak film. density OHcould The were

reduction in the

be analyzed. peak cd, the with

Sn present the total velocity

potential, to

charge,

charge and

analyzed using

respect

dependence technique. Varsanyi, buffer Vfmin). rrence using

sweep

concentration

the

potentiodynamic

et al. the

[71r] made

some

measurements at the high

on the

passivation rate (9

of

Sn in

borate and 3.6

potentiodynamic important peak of in the of (b) at

technique feature of

scanning

V/min, was been this buffer: to

The

most

potentiodynamic (vs SCE), which the

curves had not of

the

occu-

of a current The

at about the situ

-I LB0 mV film

previousfy potential (a) the mV) and

observed.

nature using at

passive

formed

in

vicinity In borate

was characterized passive film formed

Moessbauer negative amorphous more positive

measurements. range of potentials or

more

(-1180

-780 oxide

was duplex, Sn02 only or

consisting

highly the

Sn(OH)

hydrated the

stannous layer

Sn(OH)4;

poten:ials, a more

passive

consisted

of S&V)

hydroxide

or oxide

which

ensured

efficient passivity al.

passivation. of Sn in The 02 neutral

Potentiodynamic phosphate of thin buffer transparent trnnspassive measurements between cathodic at Ecor Ip were

and cyclic (PI-I 6.7) were

voltammetric carried nut

studies by

on the et film,

Ammar

[75].

formation ovnlved

electronically range, was

conducting indicated. from gave low -1.2 one scan of the the The

passive solution 2.5 V

on which

was

in the namic rates two

remained (SEE) In these and the

clear. backward reverse peaks

Potentiodyat scan

performed 100 mVfsec appeared rates. and at

to

1 and peaks higher (forward

anodic rates,

peak. and

scanning, disappear corrosion the anodic work data in

two

completely potentials peak neutral used to cd

Values reverse), The iodide

open-circuit peak

potential, Ep, the

the and

anodic were

potential with

recorded. bromide, the

results and

compared solutions. constituting

previous

chloride, predict

sulphate species

Thermodynamic the anode film.

were Cyclic

possible

oxidized

16 voltammetric O2 evolution, measurements and in were carried out in the potential ranges in all between in at scan rates While O2 range between H2 and

limited peak was

potential detected results

between a short evolution,

1 and 200
arrest two and a distinct -1.2 linear, and and Linear nature predicted of Sn(OH)4 from

mV/sec. cathodic cathodic

One anodic peak peaks

cases. H2 and

appeared appeared of Ip

in the up to against

100 mV/sec the square for

the results of scan

taken rates

between were

-0.224
indicated relations of the

v.

Plots

root

diffusion-controlled were anodic observed processes. for

kinetics

the

reactions

initiating the and

passivity. irreversible was

Ep -vs log (scan While the

rate)

indicating of SnO

formation negative than

Sn02

from

thermodynamics at

at potentials more

more positive were

than Ep, the formation Ep. The conclusions

was predicted the results

potentials

obtained

of the two [76]

techniques

generally

the same. to investigate the structural changes ele-

Albu-Yaron during ctron the

used electron of tinplate used to

microscopy passivation study the

oxidation

films. structure

High of

voltage relatively when

transmission thin tinplate

microscopy

was

specimens, passivation

especially films were

for the analysis heated

of structural

changes

occurring

in 02-rich of tinplate

atmospheres. passivation were considered methods New related by Azzerri reported and in the Cerboncini literature sugges-

Some [77].

aspects

A critical the

assessment tinplate

of the experimental layer

for studying ted by the of

passivation Electrochemical film.

was given. were the

Approaches to of the some

were

authors. the

results Moreover, treatment

semiconductor process properties parawas

properties maters

passivating

influence final

in the

cathodic

dichromate cell

on the

tinplate process. on Al the

examined.

A circuiation

was designed

for the passivation Sn films between in

The eIectrochemicai by Chen et al. [78].

behaviour A

of plasma-formed was made

was

investigated Sn rest

comparison Sn films,

plasma-formed with: (i) the

films

and the (ii)

conventional cathodic

particularly (iii) anodic and film,

connection

potential, vation

polarization, (iv) auger

polarization (v) fine

leading The

either unique low

to passiphysical porosity)

or to dissolution, properties

analysis, in the

corrosion. grain size,

and chemical

(C and 0

and

of plasma-formed chemical behaviour.

Sn were

found to play an important

role in modifying

its efectro-

(IV)

CATHODIC Studies were

PASSIVATION made its by

IN DICHROMATE Racquet It ff rom and Aubrun [79] on that sulphide such H2S during Chemical suggested staining could inside arise

tinplate from a

cans

and

prevention. Sn 2+

was

suggested

stains or heat

reaction

between

5n

dissolution)

and

HS-

resuIting

from

the degradation
protection

of amino
by cathodic

acids

or similar

compounds

sterilization.

Staining mical

treatment of

was discussed. were

and electrocheby the authors as

production

of surface

oxides

Sn and Cr

17

a method authors solutions

of found were

protection that very the

against Cr films in

dissolution, produced preventing

and by

consequently cathodic

against

staining. in

The

passivation The

dichromate to staining

effective

staining.

resistance

was directly

related

to the amount et al. [ED]

of Cr on the surface. the cathodic method of passivation The were of Sn

Parkhimovskaya in 25 gram mental ribed. the

described at

Na2Cr207/liter including

solution current to

a pH value flow

between

4 and 6.

experidesc-

conditions The

density, the

rate, of

and temperature passivating were coatings very

conditions amount

leading of Cr

formation

containing resistant to

optimum

were

indicated.

Such coatings

corrosion. Studies the The that A anodic were made by Rauch of tin and Steinbicker plate passivated [El] on the reactions cathodically in law. OCCUrring during bath. showed

polarization products film

a dichromate The Cr. electroplating using the results

oxidation

were

ascertained a large Berlin lines,

using Faradays proportion [82] for

the passivating procedure sheets was

contained by

of metallic automatic

described

of

Sn

on steel treatment

in industrial

plating

followed

by passivation

cathodic

in dichromate

solutions. et extent al. of [83] on the effect of Cr content in the

A study was made passive layer by the of

by Staronka on the

tinplate method The

sulphide

staining.

Passivation

was made in

cathodic

and by the total The

method of

of cathodic metallic were

and anodic Cr in

polarization in the

a dichromate layer were

bath.

amounts passivated

and trivalent immersed The

passive

determined. then

sheets

H2S04/Na2S203 of sulphides content in

solution,

and were on layer. the

subjected was

to cathodic found to

reduction. with best

amount Cr

precipitated teh were A passive

sheets The

decrease to the

increasing

conditions

leading

resistance

against

corrosion

described. mechanism of was proposed by Rauch based and Steinbicker [84] method for the cathodic by the

passivation authors for

tinplate

by K2Cr207, the role

on a practical Cr in cathodic for

developed

evaluating

of metallic of

dichromate adjusting the

passivation. commercial to oxidation of con-

The authors passivation (dissolution) ventional cal cally

discussed the treatments

importance the

their

results of

to improve staining.

resistance The passivity

passivated and corrosion [85]

tinplate

and sulphide

resistance

tinplate

was improved

by Jargon containing

and Maschke Cr.

using an electrochemisheets were electrolytitime, a to

treatment tinned,

in an electrolyte followed an by heating

E 3 steel point a Cr

above the

melting in

of Sn for bath.

a short

and then passivating corrosion. cathodically scence

applying layer

electrochemical

treatment and the

This

produced

containing [i36]

25 mg Cr/m2, the

layer

showed

good resistance

Britton

examined of

surface acid

layers

formed

on tinplate

passivated fluore-

in a solution to detect

chromic

or sodium acid,

dichromate, alkaline

by X-ray

in order

the residual

Cr after

and anodic

treatments.

18 The authors in detected H2S04 or two by main anodic or-containing oxidation, constituents: and The (ii) the of (i) other Cr which was was two

dissolved soluble

constituent for the

in concentrated were

alkaline

solutions.

methods

analysis

constituents The effect treatment effect of in

described. on the composition was on of the by fiim formed on Sn by cathodic et al. curves [E7]. of Sn The in in

of anions dichromate was

solution both

studied the

Subramanyan polarization tin the

anions

studied

cathodic of

dichromate dichromate potential that the

solution solutions. range. film

and on F-,

the Cl-,

anodic and effect

oxidation

cathodically current

passivated over the

SO:was

increased found with

entire found SO:-. oxide poor

The

opposite

PO:-. like F-,

The Cl-, that

authors and the and

composition [Se],

was altered

greatly et

by anions al. [87] for the

In another film

publication

Subramanyan was

observed

tin the

developed

on Sn surface lacquer

responsible They

discoloration that

adherence

of subsequent

coatings. solution

found

a pa&v&ion of the

treatment

of pure Sn foil ssary PO;-, film Ffor Ciwhich and PO;the

in 5 % K2Cr207 adherence of

adjusted

to a pH value The effect found of

1.5 was neceanions SO:-,

lacquer

coatings. Cland SOithat

and F-

was also studied. at potentials retained

were of Cr

to produce

a yellow with

was stable the

below its

deposition. of the of

However,

surface

brightness. passivation

Results

potentiodynamic the above anions

anodic were

polarization also given.

of Sn after

cathodic

in presence

Soephenberg tion of cathodic a model properties ted oxide reached of Cr, of for the

et al. [89] dichromate formation

investigated passivation of the

the films

kinetics

and mechanism tinplate. following The the a

of

the

formaproposed of the

on electrolytic coating

They study

passivating

of the coatings three stages: (ii) (i)

and the an

kinetics

of their period until growth the

formation. which surface higher of made

kinetics reduction

consisof of Sn

incubation

during the at

took

place,

iogarithmic and (iii)

growth root with

concentration surface the

Cr

6- 10 mglm, and the this stage

square

concentrations species following current

was

associated Dichromate 25 g/liter;

diffusion was

reacting the 4.5,

through

porous

layer.

passivation bath

under pH time Auger

conditions: density

Na2Cr207.2W20, (charge [90]

temperature

55C,

400 A/m2 et al.

density

400 couiomb/m2), ion mass layers

and treatment spectrometry, produced

one second. and photo-

Leroy electron treatment. total verse the Cr,

applied to study

secondary the surface

spectroscopy

on tinplate

by chromate such es transby using were of

The study was made Sn, and 0, of

to perform some in the

in depth

analysis

of elements The chemical

and to detect each of element the

external

pollution. layer

distribution imaging

passivation ion mass to

was obtained

facilities using

secondary

spectrometer. the

Attempts oxidation

aIso made

photoelectron by chromate

spectrometry passivation

determine

states

the Cr included

treatments.

Pennera ctrolysis the

1911 described

an aging bath. Cr

process

in the

passivation the validity that

of of

tinplate the

by

elefor

in a dichromate of increase during film, and the

After metal, Cr found its

confirming the author

method

determination in the

showed

the

aging film.

process Increase of the

resulted of

in metallic aging (ii) was

in the to: final (i)

cathodic

passivation the

temperature

accelerate of

formation Cr. The

passivation

increase

content

metallic

mecha-

nism was described Saijo, the et al.

in detail. studied of the effects of cd and the solution and amount by of charge used in

[92]

cathodic

passivation

tinplate emission

in Na2Crp07 spectroscopy of

experiments microscopy. Cr oxide, volume

involving The oxide meta-

anodic

dissolution, film More

electron

electron hydrated

passivated and Cr. llic

was found to consist than half the of this film film. The

3 components:

Cr of

was hydrated total amount

Cr oxide.

The

Cr was <5 % of

of Cr in the the total surface

dichromate-treated of the dichromate deposition

tinplate treatment. of Cr.

showed a parabolic The hydrated

increase Cr oxide

upon increasing formed on the

charge

prevented

The Cr oxide solution the at

and metallic pH 7.5, film

Cr were dissolved by anodic dissolution the hydrated with oxide did not

in deaerated The on

phosphate surface of

while

dissolve. films

dichromate

was described

and without

Sn oxide

the tinplate, Pawel and Guetlbauer [93] studied low the cathodic in passivation Na2Cr207 and other of tinpiate and the formed passive The

e~ectrochemically layer

on cold-roIled, for its

C steels resistance

bath, surface

was examined

corrosion

properties.
The of

passive layer
of temperature, layer ws

was found to consist

mainly
of

of &ompounds of Sn and Cr.

Na Cr 0 on 2 27 were expressed the in fomtion mthmticai

influence

pH and concentration
also studied.The results

the

passi-

ve

relations.

Albu-Yaron samples

and

Smith

[94]

studied tinpiate

the

structure

of

the

passivation

film

on

of cathodically By using

treated ring

in dichromate patterns, (tetragonai Single of the

by using transmission structure crystal

electron as as

microscopy. mainly lower

diffraction Sn02 film.

was identified as well patterns Cr and

f i ne grained oxides of

poiycrystaIiine

structure)

Sn in a continuous evidence structure). [95] films applied formed for

crystal B-Sn,

diffraction metallic

were Cr203

recorded, (hexagonal Fousse nature was rent

showing crystal and

particles

metallic

Oarre

magnetic on tinplate

measurements by di~hromate the magnetic

to

characterize
A

the theory diffeand

of passivation which studied

treatment. behaviour with of the

advanced patterns

explained and the film.

simultaneously variations For tinplate the the

the nature

of varnish passivation

adherence

aging of the solution was the with

passivation cathodic

by immersion

in a dichromate during aging The final

treatment, of

principal varnish more

phenomenon hours

observed after the

maximum of

adherence varnish

several

passivation. amount of

improvement

adherence

was

important

than

20

metallic cule

Cr in the

passivation of the

film.

This layer

method

allowed

the

orientation and rapid

of

mole-

and radicals

superficial

to be studied

by simple

physical

measurements. Auger analysis of the [ 961. surface The passivation of layers tinplate on tinplate and thinner The depth of was made in by Grande

and Johannessen bath than during those

passivation in

blackplate and profiles Sn by less

a chromate layers

polarization on alloy

resulted

considerably steel.

defined

tinplate [97] of

and Sn-free reported chromate, on the

were

discussed. treatments results were

Bijimi in aqueous

and

Gabe

passivation and

cathodic The

solutions for a range

molybdate pH 5-9, The process were of

tungstate.

compared tions

of conditions: 1.0 M.

temperature was

ZO-60C, using

and

concentraand content solution,

between

Cl.01 and techniques.

assessed using anion time.

polarization The Cr in of

coulometric was (ii) found pH, (iii)

The with charge

films increase and

analyzed (i) the

ESCA. concentration Increase than of

to

increase process effect. contained

(iv)

treatment were small

temperature and and tunghexastates which

had the state valent of the

opposite and

Chromate trivalent

films Cr with

thinner

molybdate Cr the metal

films, Cr.

amounts only in the

The molybdate The of

and tungstate both

films as metal

contained and

hexavalent state,

metals.

Sn existed divalent

oxidized

was a combination

and tetravalent

Sn.

(V)

ELECTRODEPOSITION, Results of electroplating [9S]. The

ELECTROPLATING Sn from

OF Sn AND bath on

Sn ALLOYS. were the reported bath and by Purins as and as The

a pyrophosphate was dependent

and well the

Vitina

reduction of

process the film. to S&V)

conditions hydroxide, passivation

as on the formation by

decomposition of a passivating of Sn(II)

Sn-pyrophosphate The authors

complex, spoke of

cathodic film S&V)

caused influence

oxidation of various

together electrolyte was

with

oxide

formation.

variables on the

including plating the

stability, investigated. Combined degree

concentration, hydrochlohydra-

and bath ride zine The This over was

stabilizers found

process

Hydrazine with

to eliminate resulted bath very

oxidation surfaces efficient

of Sn(II). of a high in

gelatin, and of

hydrochloride pyrophosphate bath a wide Azzam et was

in tin was very

of purity and tinning

smoothness. Fe Sn sheets. plates

Sn plating and

stable

towards

hydrolysis,

produced

pore-free

range al.

of temperatures. [99] studied during for the galvanostatic of polarization Sn from transition bath alkaline of the of a Sn anode stannate Sn anode and the films the two baths. and 2

parallel critical with

Cu cathodes current increase in

electroplating the

The

density NaOH A

active/passive increase in

increased in Na and

content,

temperature, curve showing

decrease ascending formed Cu

stannate descending surface

content. portions

generalized with

potential/current the colours potential of

together The

the of

different each of

on the

was

suggested.

cathodic

electrodes

was characterized final slow change

by an initial in potential

rapid with

rise

to more density.

negative Linear

values, Tafel

followed were

by

current

lines

obser-

ved for the cathodic The influence of

overpotential. sinusoidal alternating and Fawzy current [ 1001. on the behaviour a.c, of tin-plating

bath was reported on the from cd on both

by El-Rehim anodic

Sinusoidal during The the

was superimposed of Sn and more

and cathodic with two

potentials cathodes. cathode

eiectroplating of the

a NaOH-Na2Sn03 polarization affected. as the a.c. At

bath was

effect to

a.c. on anodic anode was was

cathodic greatly rease

studied.

The

nearer

a given direct

cd the

electrode

potential

found change

to decin the

increased. between

Variations the individual

in the

electrode increase

processes, in the

distribution ion ratio, The

of dc

cathodes, were

metal

distribut-

and decrease reduction of was

in cathodic Sn on a by

efficiency electrode et

discussed. complex The III solutions effect of during Sn

solid

from al.

electrodeposition citrate, ion and

studied

Shabanova

[ 1011.

tartrate,

and oxalate polarization

ions, ethylenediamine, of Sn was

and compiexon The

on the

electrodepositin the of the Sn

investigated. citrate, in the

polarization III and of 1.0,

increased

order:

tartrate, led of

ethyienediamine, to a decrease crystalline

complexon mean diameter At

oxalate. grains

Increase and to the

polarization formation

the

fine

dense dense, of which

deposits. bright

pi-! =

about

98 % of

was deposited at 30C.

in a uniform,

deposit. an oxalate either of

Electrolysis solution to the

was best was

conducted by of of

Electrodeposition polarization, ions of

Sn from

accompanied discharge surface surface. In

high the

chemical complex

was related formation

inhibited film on the

Sn or to the

a passive

the Sn electrodeposit Aubrun electrolyte ecule [ 1021

, or to the adsorption
on electrolytic extraneous and

of oxalate tinning chemical of The in

on the electrode an agitated

reported

medium.

an

containing from

a mobile a brightener

species, being

eg an ion or a moieat the the interface, interface

coming

capable

adsorbed

agitation

was found to enhance species were

adsorption. reflected

interactions

between

and the chemical ing including actions were

in many

characteristics of

of Sn electroplatThese for and the inter-

the polarization interpreted notably

curves

and the

morphology

deposits. models Lucke

on the basis of those proposed

previous by Chan

mathematical (1962), by Aubrun Two and

electroStuewe polari-

crystallization, (1963, zation ions with made 1971). curves were

A quaiitative of

model

was developed in agitated of

to describe crystalline in good

Sn electroplating The results. author,

media. the model

modificatagreement was also descriadsorptelectroof Sn in

distinguished.

predictions Another

were

the experimental by the same

investigation Two of the the series

on the

same

subject were the

Aubrun

[ 1031.

of experiments cd range occurring for

bed to shed some light ion process which plating

on the existence to explain The

optimum phenomena of

was proposed media.

during

of Sn in agitated

mechanism

electrocrystallization

22

a phenolsulphonic disk and electrode. the impedance species deposits as the

acid The

bath

was

studied

by

Aubrun plotted by the

et under

[I041

USing

rotating

current/voltage were

curves explained

steady-state of at of

conditions, least the in three three this

diagrams at the

coexistence The

adsorbed kinds of

metal/electrolyte spongy, compact, The

interface. and dendritic suggested surface H

morphology were of of

were: c-d.

which

formed

sequence lytic step

increased. at the

authors with the

a coupling diffusion

an autocatasuch sites as on

occurring These

interface

adions

Sn ads+. the surface.

adions

competed

with

adsorbed

atoms

for

adsorption

Polarization et al. [105]. Ni-plated weight

during The

tin

electroplating of

from

salt

melts

was measured for a steel containing (FeSn2 uniformly, or

by Delimarskii and a

results

potential/time Sn plating At first,

reiations from

electrode SnC$ Ni3Sn4) and

steel (20

electrode

during

a melt layer spread

+ KC1 was to

%) were by

described. Sn

a transition did not

formed

followed

deposition.

FeSn2

led

non-uniform A study ing organic of

plating. on the oxidizing electrolytic agents deposition was acid performed and its of of tin by from an alkaline and solution contain[I&]. The

Smirnova, products

illyuvieva examined,

behaviour with tion than of to the its the of

m-nitrobenzoic of the

reduction these shown of

was

together

variation Sri. The

composition of the such by

oxidizing to occur

agents at

during

electrodeposiless the positive products Attempts g by using

reduction with

Sn was reduction

a potential acid and

those

associated

m-nitrobenzoic azo, and hydrazo in

incomplete the

reduction Sn yield separation study The

as azoxy, the

compounds. the cell,

increase

dividing

electrode in the of cell.

spaces

appropriate

of electrodes of the author surface

A photo-electron by Duncan [ 1071. in

a tin the to

plating importance

bath of

anode the

was state

reported of the the Sn

emphasized In than order

anode must mm

surface dissolve

electroplating. rather

ensure The

uniform anode

deposition, was about to

as stannate a larger

as stannite. Sn which The potential the of film Ni Al Ka

8 square a filming and 1.0 eV. The

cut

from by

sheet by K with

of pure

was previously bath of was 4.5 x-ray V, with

subjected M Na

process 0.38 A/cm, The

pretreatment at 333

polarization. a cell was terms surface use of metals of: A

0.58 and

stannate of of in about 1486.9 eV.

M NaOH The results of

a c.d

exciting were

radiation in

energy expressed

reported

binding

energies

presence Klinger Au and

and Na in the the

was confirmed. base-Sn alloy coatings contacts. as The a substitute Parkinson (50), using of and 40 this for bath NaF

[ 1081 studied other more the was instead

expensive composition

for

electrica (250),

(1951) (50

having

NiC12,6H20 later

SnC$.2H20 of this bath

g/liter)

first of

used. NaF was

modification The

g/liter Ni-Sn

NH4HF2 electroplate

employed.

corrosion

resistance

to H2S was discussed.

23

Electrocrystallization investigated forms curves and bath results of by rectified reported. currents with Lavrinenko

of

Sn et on Sn

under al. the was

non-steady [109] nature who of

state examined cathodic in

electrolysis the Sn effect

conditions of

was

different

current The

deposits. using

Polarization d.c., j-phase, The used, and main the

were

deposited

a Hull from baths

cell

single-phase was H2S04

as

well

as pulsed additive. compared.

forms Other

a generator. were also

a brightener baths were

with

different Co., of

Suwa a bath

Seikosha consisting

Ltd citric

[I 10] reported
acid, the KAu oxidation

on the

electroplating and the

of

Au/Sri

alloy

in

was described alloy ing

to suppress the

cyanide and SnC12, 2+ to Sn4+ in of Sn (Pd) by

a practical Au/Sri in the

system

electroplated electroplat-

by isolating cell.

nonconsumable

anode

a diaphragm

Nawrocka electroplates concentration thickness were phases storage. centration. Noninski renewal of of of

[ 11I] was able

for use in the the and the

to

prepare

uniformly industry. of HBF4

thick The played

deposits total an metal

(plates) (Sn and role

of

Sn-Pb Pb) in ion the

electronics

concentration At low

important the

electroplate. 35-450 beta).

metal The the ratio

ion

concentrations, were phases

best

results of 2

obtained (alpha The

with and

g HBF4/liter. Change of the was in

electroplates of the with two

composed occurred of the

upon

microhardness microhardness Petkov electrode electroplate. Strong continuous

plates also

increased

increase presence of

Sn con-

The and the

affected the

by the effect

of surfactants. mechanical composition

[ 1121 surface

investigated on the effect

continuous kinetics and of alloy

electrodeposition was studied by

a tin-zinc

The

means during

a self-cleaning electrodeposisurface. more at The negative lower Zn

rotating tion due

electrode. to the

depolarization mechanical of

was established renewal the of the

electrode the rates,

continuous component, concentrations, Soloveva electroplating slow stage

mechanical Zn. This

regeneration increase was free

surface at higher

increased renewal

greater

and at lower and Krasikov

KOH

concentration. on the nature The transfer of polarization indicated two electrons. of of was Sn the during that tin the The from ions

[I 131 reported
with of the

from was

chloride-fluoride

electrolytes. simultaneous

results of

associated the

authors chloride being

discussed and reduced.

nature

polarization as of

during well ligand as

electrodeposition the composition by OH-

fluoride-chloride The chemical the slow al. [II41 Al in them the

solutions, processes stage. a study and

replacement

sugges-

ted to precede Vertes deposited of Sn-I I9 et

electrode reported alloys this was

on

the

chemical with Cu.

state The

of

the

tin

layers effect and an onto

on various was used

electroplated The interaction

Mossbauer Al Al alloys

study. also

between The Si

several of

Sn deposited important role

onto in

investigated. at the

content Cu

played

intensive

alloying

interfaces.

electroplated

24

the alloy

Sn electroplate containing

formed 17 % Si with

an alloy was the found Al

with to

the enter

latter. into in a

The more

Sn deposited intensive of other

on

the

Al

association, Al alloys

presumably studied. Steel -al. [I 151. with

alIoying

substrate,

than

the

case

sheeting Good 0.22

with

an extremely and

thin

tin

coating

was

prepared by layer

by

Kuroda

weldability to

glazing Sn, and Cr.

adherence then

were

obtained

electroplating of the hydrated manufac-

a steel Cr oxide ture

1.12 g/m2 0.5 to

applying

a uniform

containing

3 mg/m2 tin cans. alloy

The sheet

was then

used for

of corrosion-resistant An electrolyte of 600-650 Sn salt g/L) (6-10 was for

lead-tin

plating

was

described g/L surfactant (4-10 of

by

Purins to and for

et

al.

[I 161. (27-33 gum

Addition g/L), (0.8-1.5 with

g/liter g/L), found Various for

K4P20, resorcinol to increase

and 0.35-10 or N2H4.t-U the were iron

a Pb salt hydrolyzed

g/L), the bath

stability used. was

electroplating

Pb/Sn Another

alloy.

surfactants tinning

electrolyte

sheet

described of the as

by

Katser

et

al.

[f 171.

The by to

tinning adding the bath

was simplified 2-5 g/L

and corrosion

resistance acid

electroplates

was increased additive acid (65-90

B-naphthosulphonic Sn sulphate

alkoxylate g/L) and

a surface-active

containing

(50-60

p-phenol-sulphonic

g/L). Vertes containing solutions, solution, the wet et Al. and followed was al. [Ii81 The then by studied the were electroplating treated Sn with the Cass found the into of Zn with layer Cu and to and of NaOH was Sn. samples and of Mg, Si, or Cu

samples an

HF-containing in alkaline

HNO3 Na2Sn03 of

intermediate

formed The

electroplating with

corrosion and those thermal

resistance an of accelerated other

deposits

checked test

Corrodkot

tests, to by

heat-resistance deposits. to of Ni, 15OC but

and was of

be equivalent was at tested 20Cf.

inter(samples to

mediate heated that the which

Adherence were inferior of the

layers water

shock was

immersed to that the of

Adherence fayers. In

superior to elucidate

intermediate were

order

mechanism indicated

adherence, formation

deposits Cu-Sn

tested

by Sn as

Mossbauer an

spectroscopy layer

compound.

intermediate

was advantageous A new

in the of

case of tin-nickel

Si and Ku-containing alloy deposition

alloys. from bath was pyrophosphate used because baths the The was usual pyro-

application by had Enomoto so many had

described Fbath

[I 191.

The

pyrophosphate such

disadvantages

as corrisiveness high throwing smoother

and

toxicity. better

phosphate a more and the tions layer

bath moderate capability found the

several

advantages, temperature bright circuit gold.

e.g.

power, and

ductility, plates, Applica-

operating of obtaining in printed

(50C), plates

finer-grained additives.

at low and in

c.d without electrical

were for

boards,

contacts

as an under-

very

expensive

Electrocrystallization by an oscillographic tive [120]. surface tion of surfactant The layer desorption

of technique in

tin

under

nonsteady-state the formation for bright

conditions and degradation tinplating by

was of

investigated an adsorpet al. the

to study

a sulfate was studied

bath

Loshkarev

oscillopolarographically of a drop in current, the of time Sn The needed from cathode

of surfactants as well

from

of an electrode the adsorbed The

at the moment layer to estimate

as the

reduc-

for

establishing bath a Cu

adsorption the was

equilibrium. complex coated

electrocrystallization (Dneprol) of bright was studied.

H2S04 was

containing foil which

additive with

a layer

Sn at a cathodic were observed [IZI]. was

c.d of 2 A/dm in the A

for 5 minutes. of tin alloys of the Sn Cd

Some kinetic with the cadmium cathodic

characteristics by Solveva of and Cd-Sn

electrodeposition change by in the the

Krosikov alloys

composition ratio of of of

deposits of the

observed The

varying of the

concentrations in alloys ions were plotted. NHLF near other with

ions being electrolytes

reduced.

kinetics relatively of the of

codeposition

Cd from

containing curves

low

concentrations of the Sn of ions

studied. The

Partial

polarization baths - 0.72) the

discharge (0.03-O.l), In the high,

were

electrodeposition Clquality (0.6 of

consisted

Cd

(O/2-0.27), potentials scales or

(0.820-l-104), -0.6 V, the

mole/L was

at pH 3.5. sufficiently

range

alloys

without

defects. dependence of the degree H2S04 of bath brightness and the adsorption et of al. brighteners

The

in tin electroplating study (90), m/L), HCHO tion was conducted leveling (II) agent

from

was reported

by Medvedev (I)

[122]. The
H2S04 (IO

in baths of the VA-20 H2S04 (5 g/L), (90),

following. 35 OP-10 were

composition:

SnS04 40

(50),

% butyne-1,4-diol (5 g/L),

(SO),

% HCHO

SnS04

(50), The

35 % butyne-1,4-diol at 0.08-0.1

(110),40% Polarizadegree of

(20 ml/L). curves were

electroplates Bright

obtained were

I A/cm2.
when the

plotted.

electroplates %.

obtained

adsorption A parts Al

of the brightener was made Co on

was 21-25 the Ltd, with

study

electroplating Japan

of The

Al-based study to

alloys

for

automobile Al and an was

by Honda were

Motor

[ 1231.

was patented. give a material Thus, were

alloy

electroplated

Sn or a Sn alloy automotive

which

corrosion-resistant autombile to a I:4 in 100 h. The hydrogen parts

to an alcohol-containing were plated with

fuel. which

cleaned

Al-alloy

Sn to give products for > 500 h. The

corrosion-resistant were corroded

MeOH-gasoline

mixture

nonplated

parts

absorption on iron for were

during

electrodeposition

and

hydrogen et al.

charging The

of

Sn

and Cd coatings ctiveness terms were

investigated H

by Zamanzadeh by the

[124].

effein

of deposits

decreasing

absorption and the

substrate

was discussed effect. of of

of a surface presented a Fe for

or a catalytic the extent of

effect H

well-known during

barrier

Data Sn or the Sn was

absorption during

electrodeposition H the charging catalytic

Cd onto

substrate,

and subsequently The

electrolytic that

or the Cd-coated

Fe membrane.

results

showed

effect

26

unfavourable corrosion ion

for of any

increasing exposed

absorption. base to the with H of

This the

behaviour pores effect and by

favoured the both effective of steels. A in

decrease H absorpt-

in

Fe at the due

cracks.

was significantly to their were

reduced

barrier

Sn and Cd in than The Cd.

proBoth

portion coatings diffusivity brane the

thickness effective

at >, in

1 pm,

Sn being embrittlement

more

reducing

effective memreduce

of H in both was

Sn and

Cd electrodeposits to measure the

was diffusivity

compared. of H

bilayer to

technique

proposed

order

time The

of measurements. morphology al. were tests. [ 1251. made of pulse-electrodeposited acid SEM, baths X-ray contained diffraction, was Sn from SnS04 as acid with well baths and as was without throwing average duty described additives. power c.d cycle pulse of and duty at time by

Lam

et

The by

Studies pinhole cycle constant

The grain time.

size of Sn deposit The grain the grain cycle, unit or size

dependent with

on the decreasing with

and

pulse

decreased was

cd.

Furthermore, cd.

size

reduced because

increasing increase

at a fixed tial. deposit the For

average electric

and duty per needle

mainly pulse spot-type.

of the

overpotenthe changed Pangarovs with by d.c.

charges of the

higher

than

10 milli-coulomb/cm*, the average c.d with

was either

Increasing [lUllin power

orientation Pulse The duty

of Sn deposit plating minimum cycle. of et al. and ratio quality of did not

in the

order

of [LOO], throwing

agreement as was

theory. plating. ing the The reported containing of pH, the

improve of

the

compared reduced

thickness

pinhole-free

deposit

decreas-

electrodeposition by Orekhova pyrophosphate and molar and the

tin-bismuth [126]. mixed the of The

alloys

from

polyligand of Sn and Bi was (e.g.

electrolytes from

was

codeposition complexes agent alloy and

electrolytes The effect on

metal

investigated. Trilon B) and was

cd,

complexing obtained combined

ligands

composition of

the during

electroplates individual

established. of Sn and

The nature Bi

polarization

deposition

was described. Corrosion protection of steel by plating with: et al. et al. by [127].

(i) (ii) (iii)

Sn layers

was reported by V.A. alloys

by Katsuhito, Paramonov was

Cr was studied Sn/Zn Tokyo and Koho was Ni/Zn

[ 1281. the

patented

I Nippon

Steel

Corp.

Jpn.

Kokai

[129]. proposed by Darken [I301 for the graphoepitaxy of electrode-

mechanism Sn.

posited

(VI)

ELECTROCHEMICAL The effect

was

PROPERTIES in plating et

OF ELECTROPLATED baths al. on the brightness Sn-Zn

Sn ALLOYS of tin-alloy was plated electrofrom

of

additives by

plates

studied

Aotani

[ 1311.

alloy

tetrafiuoroborate ness of IO p salt

baths.

The

deposit

on steel

contained with

80 % Sn and had a thickit did not rust in the or Cu The con-

When this deposit spray test for

was treated

chromate The alloy

continuous plating

300~-400~ 60 -

hours.

deposit highest

on steel solderability. the bath

substrate

containing alloy

about

80 % Sn had the almost

composition tained 70-80

of the

deposits

remained

unchanged and c.d were

when kept

% Sn and the concentration and Kuzovkova with [132]

of HBF4 on

constant. of steel

Kuznetsov USA

reported Bi/Sn, ti2S04

the

cathodic alloys.

polarization The hydrogen A

electroplated were

Sn, Sb/Sn, in 1N

and As/% on the

evolution decrease and Sn,fSb. The by Sn

potentials in these

measured

electroplated Sn /Bi,

ailoys. Sn, Sn/As,

potentials of

was found in the following the polarization of the curves preliminary for

order: these

The behaviour effect was

electroplates hydrogen

was described. absorption

also studied alloys

electrolytic potential and [ 1331. some

and its binary The

on the cathodic of by

evolution

of hydrogen. gold-coated The authors tin-nickel proposed alloy the Thin of and

corrosion

resistance studied

worn Antler

tin-nickel et al,

electrodeposits formation

was

of a thin

passive film

of Sn oxide

with

Sn and Ni resistant.

hydroxides. The formation Ni3Sn4

electrodeposited deposits Ni3Sn2 wear, reach of was but it both

Au on Sn/Ni single phase

alloy (SnNi) The

was also corrosion and multiphase film

mixtures be

of

SnNi, by

also suggested. sFontan@ously thickness.

protective taking

could

removed at room

mechanical to in

reformed The

1500 h in air of Sn/Ni Similar Sn/Ni to

temperature was restored

a limiting after were were

resistance

corrosion

less time, of passivity

only a few days of aging. made with freshly etched plated

observations on Cu,

of the with

development aged deposits newly wear was

deposits before

of Cu which fractured

chemically

immediately When the

exposure, was of

and with exposed the by

edges

of Sn/Ni

electroforms. the

substrate resistance by aging. the

Or by brittle determined The coatings

fracture

of Sn/Ni,

corrosion

material

by the substrate, method

and was not restored was with The used Sn/Bi anodic change which for

potentiostatic

studying of

properties of 4,6,9 in

of and

metallic 20 pm

of brass electroplated et al. rate [134]. of

alloy

thickness curves

by Frantsevich, at 20C,

polarization 0.8

plotted

3 % NaCI on the

and the

potential thickness, surface

mV/second

showed to the electron

an inflection uncovering microscopy of

the curves for base anodic metal.

4 and 6 pm The coating

corresponded by

was

investigated

after

dissolution. measurements [ 1351. different during deposition alloy of Sn/Ni alloy were made by Hatai

Polarization and Lohonyai baths under pH.

The kinetics conditions

of Sn/Ni

deposition Sn and

was studied

in NH4HF2 and

of temperature, for the

NH4HF2 concentrations, (7)

A linear

dependence

was found = a-b nuclei,

cathodic

overvoltage

as a function the electrode phenomenon.

of the logarithm processes, the

of c-d. [(l/v) spatial crystal

log i 1.. and

This equation

described

the

electrocrystallization

28

The composition metallic trations

of the deposits Ni3Snq

(73 % Sn and 27 % Ni) studies showed

corresponded that high

to the

inter-

compound with

Microscopic (3)

NH4HF2

concenDecrease to Sn in

low pH values in the

gave smooth, of

uniform

and bright

deposits. of Ni

in temperature,

concentration

NH4NH2,

or in the

ratio

the bath increased

the roughness and brightness et al. [136] alloy studied the

of the plate. cathodic polarization electrolyte during with electro-

Kosmodamianskaya deposition additives during ing of of

a tin-nickel

from

a pyrophosphate during

and without and also

such as ethylenediamine, separate Ni, and deposition. Sn/Ni alloy of and

both The from

codeposition

of Sn and Ni, during

their Sn,

high cathodic pyrophosphate on the after that

polarization baths

electroplatwas during to the

without

additives

related the

to the

adsorption of Sn, Ni

P2Of;the

ions alloy fact

electrode.

Depolarization

deposition

addition this

of ethylenediam~ne characterized the surface,

bath was apparently capacity for

caused

by the

additive, ions from

by a high resulting

adsorption,

partially

displaced

P2Of;-

in facilitating

the discharge

of the pyrophosphate

complexes.

(WI)

SEMICONDUCTING The mechanisms of

PROPERTIES electrode

OF Sn02 re-establishment after Sn cathodic of the n-type non-stoipolarization polarized

potential

chiometric were

Sn oxide by

semiconductor Kirkov [137]. without

electrode The evolution After potential life-time

and anodic

investigated

oxide or

semiconductor 02, and the

was

cathodically curves time nature charge. wave. at curve of

and anodically open circuit one were

of H2

potential/time the potential/ and

measured. whose its

cathodic depended depended

polarization, on on the the

showed the

wave

concentration imposed

electrolytes, anodic

while

electrode

After

polarization,

the potential/time

curves

did not

show a similar formed H+

This behaviour lattice The

was interpreted during cathodic

on the basis that polarization by the

Sn-O-H

bonds were of

on a Sn02 and H20. an electon on the

reduction surface

adsorbed

Sn-O-H

formed at

on the

semiconductor between which

decomposed lattice not at and

through the OH was attai-

transfer

process The

open-circuit c.d.

the H2

Sn02 was

surface, A/cm2.

limiting

below the the

observed this c-d.

3.052 ned and

x l0-4

After

1 second, upon This lattice,

polarization logarithm was

potential of

a constant the nature of

value of ions

dependent

electrolyte

concentration basis of of

electrolyte. on the Sn02

behaviour and the

interpreted of the

on the

adsorption Sn-O-H. The of free

change

concentration

electrochemical carriers, as well

behaviour as the

of

thin

SnO2 of

films the

with

different Sn surface d.c

concentrations were pulsed studied polari-

behaviour

oxidized of

by Deryagina zation in the

and Paleolog system

[ 1381 using the + e-

method

right-angle at

[Fe(CN),.13-

= [F~(cN),]~-

potentials

corresponding

to

the

thermody~~mi~~l~y were prepared

stable

state

of

SnU2

Thin

SnO2

films

with

eiectricai plate. The

~ondu&tiv~ty

by spraying

a SK14

specific resistance of SnU2 could be changed 3c 5+ ing In as acceptor and Sb as danar impurities films quartz on Sn were were prepared by anodic The oxidation films

solution -3 from 10 into

on a hot

quartz

to 20 ohm-cm the SK14

by introducOxide films on The

solution. Sn02 8

in NaOH

solution. 20~0-~~~0

800-130~ nature

,8 thick. of the oxide

on Sn were

thick.

semi~ondu~tnr The anodic Shub

films

on Sn and on quartz Sn IV found oxide

was estabtished. was reported by

behaviour

of a single-crystal processes were effect

efectrode

et al. [1393. rates

Anadic

to proceed for of

on an SnO2 the transfer

electrode of charges The by the NHE), ~~th~n of

at significant from the

due to the tunnel particles which the into the

responsible band

reacting range at

conduction was a found for

the

semiconductor.

potential width as well the

tunneIing (950-70 of the anodic the

to occur

was determined above 1.8 V,

of the space charge as by the 1.5 to their

fayer

SnU2

electrode

adsorbability I.8 V, the tc

reacting

particles occurred band. in

and their mainly by

energy, the

range and the 366

processes conduction in

creation were in

holes using ( 1 = dark,

diffusion

The the

processes dark and

studied the in light the

potentiodynamic nm), and finding

technique the

i N H2S04
between

relations

capacitance,

potential

potentiai

of irradiated et al.

eiectrode, [ f40]

and the photo-effect. the anodic processes sides of on a SnU2 oxide

Chertykovtseva film lysis H2SO4 electrode. of 0.5 and

Investigated was deposited solution at

The SnO2 film M alcoholic S&I4 Anodic

on both

a Ti

plate

by pyroin 0.5 M high took higher

45Oo&. were of

PoIarizatian conducted or

was made at

f M I-ICI.
to 1.4 V, the

measuram~nts processes current of the

relatively discharge At

positive
place. positive (typical

potentiai~
Up

at which
the

anodic anodic part

water depend

chlorine

did not curve At

on potentiaf. with a slope of no thermal

potentiais,

Tafel

appeared

CL3-0.4 V excitatformatwith no

of semiconducting electron Increase Tafel of slope.

electrodes), transitions solution The

potentials

,< 2.5 V,

ion of interphase ion of holes, change

in

was observed, temperature Sn02 film

which

could Lead to the the showed anodic cd,

increased electrodes

the

a special

activity

and selectivity The effect particulaffy kovtseva rate due

to chIor~ne of alloying

evolution. additives to the (Sb and F) discharge of of on the behaviour chlorine was of a Sn02 by the electrode Chertydicharge and The

with

respect

also studied decreased current electrode to Sn. to the

et al. [ 1411. to an

Addition in for the

Sb to a SnU2 concentration were of

electrode the on free the

increase centers

carriers surface.

complementary optimum etectrode, amount the

adsorption was of

formed

of Sb additive rate of

10 atomic chlorine

% in reference decreased due

On S&2(F) passivation of

discharge

the eiectrode

surface.

30

The alkaline tance tials

semiconducting conditions were

properties examined

of by types

passive Kapusta of films

oxide and were

films

grown

on Sn under [142] high using and Both of complex the low

slightly capacipoten-

Hackerman grown at

measurements. respectively. and

Different Thin films

followed

a Mott-Schottky were estimated. of thick films

behaviour. The location

flat-band the donor

potentials level due

donor

concentrations The cracks. passive The at

was also to the

determined. of

behaviour The

was more

probably of

presence

same

authors

[ 1431 studied

kinetics

charge

transfer

between and

Sn electrodes results were

and solutions analyzed metal results of an

of K3Fe(CN)6-K4Fe(CN)6 basis of the quantum

at pH 7.5-10.0 theories agreement behaviour films, of

I-50C. transfer theory

on the electrodes.

electron between

oxide-covered

Semi-quantitative The electrochemical surface for thick for thin films. on bare

and experimental characteristic was in all typical cases, of

was found. almost metallic

of

passive the

Sn was

while

behaviour were,

n-type smaller

semiconductors than those

Exchange metal

cd values

much

measured

electrodes. et al. [ 1441 measured the and flatband positions of Ti02, several n-type

Kabir-ud-Din semiconductor Sn02, dence which

electrodes

(single-crystal Sn02)

polycrystalline the

polycrystalline depenThe plots effects caused

and chemically or the onset rise to

modified of

by determining in five

capacitance-voltage solvents.

photopotential from

nonaqueous in the For

gave

deviations in

ideality potentials. not

Schottky-Mott metal altered oxide

significant electrodes,

differences interface

flatband were of

semiconductor

energetics properties

dramatically Sn02

by derivatization. were the kinetics reported

The electrochemical by by Kraitsberg and

modified The

oxide was

electrodes of

Mardashev

[ 1451. electrodes on these This zone

effect from

studied on the

modification of electrothe

I vapours
of of

of semiconductor I-, thiourea

made

Sn02 The

oxidation activity in the

electrodes. increase

modification did not lead

increased to

the

Sn02

electrodes. planar

in activity

a change

potential

of the

of the

electrode. by Sukigara et al. [I461 to study the

Capacity electrochemical values was first the were

measurements properties observed in for terms

were of the of

conducted Sn02

reduction the

semiconductor tunnel electrode. Large cd 4+ at high overvoltages. This behaviour of Ce of excited vibrational states in the

interpreted coordination interaction

contribution the transfer

sphere. energy also

From

coefficient-electrode solvent for

potential was estimated

relations, (0.65 eV). B

between

electron the electron

and polarized transfer

Measurements at a tin potential, were dioxide and

included

photo-excited monotonically pH and theory. transfer potential The in

rhodamine with electrode

electrode. decreased with of

The with

photocurrent in pH.

increased Such transfer

increase

dependences results the were

inconsistent

a conventional an extremely

electron high rate

interpreted region.

in terms

of electron

abnormal

31

Badawy dioxide

et

al.

[I471 up to

reported

on the

electrode oxides. vapour states The

properties The

of

polycrystalline were 420C prepared

tin by

containing

10 % Sb or Ru

electrodes at

the hydrolysis ing substrates. conducting

of SnC14/SbC15 or The distribution

SnC14/Ru04 of electronic by UPS.

mixtures in the were and

on conductthe semi-

band gap of

materials kinetics

was determined of the the

films

then used as electrowere deterfor the

des, and the mined. charge of

redox-systems UPS and the

Fe 2+/Fe3+ electrochemical This model space

Ce3+/Ce4+

By correlating transfer

results, was charge based

a model on the by

mechanism the

was narrow

suggested.

passage

electrons

through

semiconductor

barrier

mediation

of the deep donor states Hong Sn02 thin et al.

in the

band gap being introduced the the semiconducting electrocatalytic various

by the dopants. property effect of of The lower an this Sb-doped electrode oxida-

[ 1483 investigated
electrode and studied oxidation film or HSO;) thin

film

for SO2 (or tion of SO2

SO:-

under

conditions. at

anodic

on a SnO2

electrode

commenced effect

increasing alkaline

pH, and a good electrocatalytic solutions. Sn02 In acidic solutions, was due to

was shown for

potentials with 2oxidation in SO3 of Pt or on Pd the

the the effect

electrocatalytic sites of of Sn02 Pt or

effect Pd

incorporated electrode from that

electrode The

exposed was

surface.

electrocatalytic electrode. analysis

electrode

distinctive

of Pt of Pd containing

Sleszynski tin oxide

[ 1491 reported
at

the

of square The

wave

voltammetric developed author

results of

at

semiconductor

micro-electrode. microelectrodes behaviour transfer. the was tunnel was at

recently by the

theory to be

square of of a

wave

voltammetry

found

capable

describing completely Da tion. formed with of

the experimental reversible [ ISO] electron

Sn02

electrodes

even in the

absence

Silva A

discussed model

effect for

at the

a semiconductor/electrolyte spatial over layer an of changes

juncwhich

theoretical

developed in

on semiconductors consideration in the the

deposited of the

a thin effect.

layer An

insulator study

substrate, was made For of the

special

tunnel transfer

experimental for effect to Sn oxide was

the

variations in which

charge

coefficients a tunnel was were

electrodes.

cases

current

resulting

from

predominant the

exchange anodic values. currents Use cd.

current, The

a simplified values

equation

developed reasonably which

calculate to be the used

resulting

thus calculated proposed great an

close could

experimental for cathodic

The with of

author

also

equation barriers.

sufficiently

potential

Sn02

in semiconductor-insulator-semiconductor [ 1511 and by Agnihotri,

solar

cells

was

described

by Sinencio

and Williams

et al. [ 1521.

(VIII)
requires

SOME

INDUSTRIAL

ASPECTS

OF TINPLATE made some on tinplate of which is enormous, have already and probably been made.

The literature

on the industrial review or

work

a separate

reviews,

32

However, publications Eggers, cans were Ni/Sn

it

is made

worthwhile

to

include

in

the

present

review,

some

important

in this field. [ 1531 found resistant that Sn-electroplated and sulphide or cathodic which for this were steel sheets or strips used Ni for and

et

al.

made

to scratching by anodic

staining

by successive

electroplaing,

followed

passivation. occurred this oxide during heat An into treatment amorphous scattered

Koer

[ 1541 studied tinplate,

the oxidation and proposed

process a

of electrolytic oxide was

model and

oxidation. contracted

formed During was

during subsequent confirmed

manufacturing, annealing, by

patches. The

crystals

found to grow on these patches. microscopy, of scales with electron different

model

metal Iography, The oxide

photoelectron form

microscopy thicknesses,

and ellipsometry. and had a tetragonal

was in the form. apparatus The

m-Sin0 of

A diagram manufacture rotating

and the description were given by

a new [ 1551.

for

simulating was

electrotinplate composed of a

Bowden allowed of

apparatus and removal

cathode

cell

which

the introduction were

of various solutions the initial use

sequentially.

Various

modes

operation

possible.

However,

for this apparatus A acetic zation form study of the

was for studying corrosion sodium

passivation of

and the lacquering in a ternary

properties. system of 70 polariin the of the tri%

resistance chloride et

tinplate

acid- saturated was performed of an equation An

solution-water al. [ 1561. The

using potentiodynamic results to were presented

by Volkova relating isochore of HOAc, of the the was

corrosion constructed

currents of

the in

composition a concentration

corrosive angle:

media.

tinplate

70 % solution

26 % solution ability

of NaCI-H20. of electrolytically by Staronka tin-plated and Choma on the sheet [157]. critical of

Characterization metal using critical

lacquering tension

surface

was performed of the

The effect surface various ments

was studied of

of the parameters of

passivation

process metal.

tension surface were

wetting were

electrolytically from H20

tinplated

sheet

Liquids

tensions out

prepared

and iso-propyl on passivated

alcohol. sheet

Measuremetal using

carried

on non-passivated, and chemical

and

cathodic,

cathodic-anodic, with

methods

of passivation. tinplate

A review

44 references coating for

was published control

by Besse [ 1581 on the use of in the (Corrosion Control

as a sacrificial edited A Cichon negative fruits already by Henry problem and

corrosion

Meeting),

Leidheiser. with direct application and to this the canning dealt industry with was the life investigated by

Adamczyk

[ 1591,

problem

relation of some of

between conserved

pressure,

corrosion compote)

in tinplate in tinplate

cans, and the storage cans. The authors

(strawberry suggested on the

developed

investigation

by Formanowicz. electrocrystallization made process in tinplate manufacture were studied of from sul-

Studies phonic

acid baths were

by Calvo [ 1601. in the

The effects of

aromatic An

sulphonic

acids on the nucleation

electroplating

Sn on Fe

substrates.

33

experimental Sulphonic was found value

method acids under on

was

devised

to

study

the

nucleation showed The

on a corroding an inhibitive of nuclei reaching

substrate. which was

well-controlled molecular the

conditions structure. of

effect formed a were and

dependent to in

the with

number

decrease the

concentration used

sulphonic These the

acid,

constant possible hetero-

concentrations adsorption

commerically. considering

phenomena ring structure

due to the atoms

surface acids. and

properties

in the

Shimizu tinplate. to evaluate rately acid

Matsushima tin (ATC)

[ 1611

reported

on

the (ISV)

corrosion tests were in

evaluation generally cans the

tests

for

The alloy the

and iron-solution of electrolytic p-d. between

accepted for steel modebase

corrosion The

resistance relative

tinplate the

plain and

foods. the tests

alloy-layer and

depended role also in be

upon these

electrochemical and by their

characteristics results. The

of steels, corrosion

played of

an important tinplate such as could ASC The

resistance

measured

means TAC

of

newly

developed Couple), each

evaluation and

methods

(Alloy-Steel-Couple), results in plain An made different of such atomic of these tests

(Tinplate directly

Alloy with

polarization process

technique. of the

correlated acid

corrosion

tinplate

cans in moderately electrochemical it possible layers layers hydrogen or to for

foods. was described under by Endle and Pethieu the on the anodic from metals. worked parts was as one a of

technique one to

[ 1621 which
influence permeability oxidation of of

study,

favourable made up of

conditions, tinplate the derived the at was

combinations hydrogen. This

of layers technique from the excellent [ 1631. repeatedly g/L

which sample,

involved was

as it

was released for studying with

the

a previously

established Tin-plated prepared cathode alkali by

technique steel Toye

diffusion

of H through resistance steel

plate Kohan

corrosion A

Co Ltd. or

tinplated in a bath

electrolyzed Cr(VI) for or the

and then and NH:

as an anode

containing

compounds or greater

0.1-100 charge

using the

0. I-10

coulomb(C)/dm* Thus, containing 1.0 A/dm a steel

anode electro-

and an equal plated with

and cd for

cathode.

plate

Sn (5.6 above the

g/m*) at 45C

was electrolyzed and at a cd

in a bath of 0.5 and

Na2Cr207 using with 0.5

(30 and

g/L) 1.0

as indicated C/dmL and little for

anode

and the for

cathode, cans for

respectively, food

was painted No

dioctyl with

sebacate fish or

was

used

successfully with al. tomato

storage. after

blackening

corrosion Katser et of of

paste

were

observed

pasteurizing. for obtaining involved of electrolytic applying a cathodically was found to a

[ 1641 described corrosion the etching

a developed resistance. solution. the

technology The

tinplates sublayer polarized occur layer due of

improved Sn from strip hydrogen

procedure on the of surface oxide of

Thus, reduction

steel to

during

etching, with

films >75

evolution on the surface

a current activated being

efficiency steel

%, and This thin

a thin layer the

Sn was

deposited the steel

freshly from

surface. its

of Sn prevented

oxidized

during

transfer

from

34

etching fusion,

bath a more

to

the dense

Sn

electroplating

bath,

thus

helping The

one

to bath,

obtain,

during the 60,

and uniform

diffusion had

layer. the

etching

in which H2S04 The

Sn sublayer Sn*+ 2.5,

was simulatneously and sodium A/dm*

applied,

following

composition: 0.25 g/L.

monobutylphenylphenolmonosulphonate at 40-45C.

cathodic

cd was IO-12

(IX) The

CATHODIC formation indicated

PROCESSES of intermetallic and Past compounds between the alkaline polarization earth of Sr(OHj2 metals and

Sn was

by Kukk

[ 1651 during

a Sn cathode and Ba(OHj2

in alkaline solutions.

solutions

of CaC12, SrC12 and BaC12 and in CatOH)*,

Elect roreduct
buffered in the solutions

ion by

of

CO2 was

performed et al.

on

rotatingtin Tafel and

disk segments bel ow and

electrode were 1.15 CO2 observed V.

in

Zakharyan polari were

[166].
curves,

Two above

steady-state results HZ0 as

zat ion

The

experimental anion, process, adsorbed and

explained donor. two steps and at the A

by

the

adsorption sm was of was

of CO2 proposed for

radical ion of anion. that the

proton

rrechani the first

the

reduct

tiich CO2

involved radical emission

tiich the

uas reduction

the of

fonnatior this

anion,

second

Photo-electron second step was

studies

the

rretaI/solutioninterface

showed

rate-determining. and Katkus [167] studied the cathodic polarization of

Galdikiene H2S04 The

Sn in

1M

solutions
polarization

containing

O-O.375

SnS04

using

the the

potentiodynamic

method.

curves consisted

of three

branches

course of which was depen-

dent on the concentration Cathodic and Skominas

of Sn/Pb alloys

of Sn ion in the bath. of tin in fluoroborate

fluoroborate plates. bath

polarization [ 1681.
on The

electrolyte
was primarily

was
used

reported for

by Bliznikas

electrodeposition and brighteners Catho14,

printing

Additives

used

as emulsifiers

were dic free of

added in order polarization HBF4

to get bright

electroplates reported

of both Sn and Sn/Pb in a solution containing

alloys.

measurements 20 g/L, necessary

were

Sn(BF412

40, H3P03 was

and formation prior to

(37 #J) 40 ml/L. polarization

Complete in order

passivation to obtain

the

cathode

cathodic

bright A

Sn electroplates. study of was made on the effect of the adsorption the of formaldehyde of this on the was to

reduction made 0.6 M,

hydrogen

overpotential

on Sn and The

kinetics

reaction was 0.001

by Kapusta and the

and Hackerman potentials (z

[169]. were curves

concentration at

of HCHO lC

SCE)

determined were given The

23 2 for the varied

using a Sn eleevolution to 11.1. on

ctrode. reaction Several electrode

Steady-state in solutions mechanisms kinetics.

polarization with were and

hydrogen from of 4.5

without to

HCHO.

pH the

postulated

rationalize

effects

adsorption

35

(X)

ELECTRON Cyclic

TRANSFER of

STUDIES mixed

BETWEEN

SOLUBLE was The Sn(I1)

Sn SPECIES investigated reduction to S&V) for the while All of was by Kadish to

voltammetry

Sn(II)/Sn(IV) and the Hg

solutions

et

al.

[ 1701 in proceeded forms of

6 M HCI irreversibly, Sn(IV)

on Au while

electrodes. of peak

Sn(IV) reversible.

Sn(II) Two Sn(IV)

oxidation The and Sn(IV)

were of

postulated. Sn(II) of

potential

reduction that for

of the for

was a function of Sn(II) was

both

concentrations, only.

oxidation all

a function processes kientics were [171].

Sn(I1) were and

concentration of the

potentials scan rate. for

oxidation Mass and

and reduction charge transfer

functions coulometric at

potential

current and

efficiencies

the by be

system Bishop measured meters

tin@/)-tin@)-tin(O) and with obtained Hitchcock Au

examined

gold

platinum potentials

electrodes could transfer V. In not

Zero-current in any

Sn(IV)-Sn(I1) Thus, referred with film Sn(IV)

or Pt cathodes the the

medium. were

the to

charge (zero)

para-

from

voltammograms Pt to electrodes be for

bromidewhose to

containing structure remove. mA/cm* The

solutions, was

were

covered This of

an was were

adherent extremely between

film difficult

suggested

(SnBr50H)*-. the reduction

Current to obtain inhibiting

densities a current action of basis tin of of

1 and 300

efficiency camphor

loss of about on the

100 ppm stages

in 0.2 M solutions. of by the process et of al.

separate was

dicharge-ionization

on an the of

amalgam of

electrode polarization

reported

Slutskii

[ 1721.
as well inhibiting ionization

On

the

results the was

and

adsorption using stages of x 10e3

measurements, a computer, the

as the action

processing of camphor

polarization studied in

measurements individual electrolyte from 2.5

on the

of

the

dischargeWith IO-*M to a

of Sn on a Sn amalgam in camphor quantity concentration of adsorbed

a supporting in solution

2 M HCl04. to 2.5 x (near the

an increase at a constant monolayer reduction pared cations, to

camphor

molecules

on the

electrode of

of surface step: the Sn blockage on the Sn+ inhibition

coverage), of the

Sn

a significantly stronger inhibition 2+ (about 70-fold) was + e of formation and discharge process The was of

oxidation/ as comcharged

observed, of singly

stage

Sn+ + e (about of the surface stages stages

5-fold). by of

The inhibition particles. process

could

be reduced action to of the

to a single camphor different

adsorbed the to the

different attributed energy

individual of these hydrate [I731

overall different

nature

and

amounts

expended

on rearranging Kiekens Sn(II) Sn(I1) et

the al.

environment. reported a The study on the electrochemical characteristics electrode which of oxidation the of

at glassy system

carbon

electrodes.

voltammetric C rotating disk

Sn(IV)/ Anodic in the

were

studied produced 20-50C.

at a glassy a single The

in 4 M HCI. was examined distinct

oxidation temperature sibility.

of Sn(I1) range The kinetic

well results

defined of

wave

examination were calculated.

showed

irrever-

parameters

of oxidation

36

Studies couples kinetic TI(I)/Pt, faradaic transfer. between NaC104. slightly point at

on

the

faradaic

rectification were in the

of made

two-electron by Agarwal charge a modified involving of of the

charge and transfer and multiple thallous/thallic K2S04, and step Jain

transfer [ 1741. obtained

redox The for of

a platinum for

interface each step

parameters and Sn(II),

electron using

were extended

Sn(IV)/Pt applicable of 0.59 the in

reactions to

theory

rectification The 0.51 The less method value and rate that

reactions coefficient solutions

electron

charge was and

transfer normal for

couple NaC104, was

KNO5,

constant of the to

the

first step the in

electron all

transfer

invariably The of of zero the the comsystem under that of

than was

second obtain the steps zero This

supporting parameters capacitance. magnitude The stable be of

electrolytes. independent The 0.1 values

applied interface of the by

kinetic layer of

electrode/solution two pared rate to constants those

and two the

double (order point system

cm/s)

were

obtained same

method. was appeared only to

stannous/stannic in eqully
HCI

was treated some specific

in the

way. The

solutions fast as

conditions. redox couple.

reaction

thallous/thallic

(XI)

PHOTO

EFFECTS studies made of the passivating films formed [ 1751. solutions of and
The of

Photoelectrochemical alkaline of solutions were

on The were films

tin

in

slightly

by Kapusta on Sn in

and Hackerman alkaline The the of

by the

photo-response studied growing of under under their

of

passivating

films and

grown

slightly

galvanostatic galvanostatic deviation

films

potentiostatic was used as

was

conditions. to a determine function

response nature

conditions from
at

magnitude

stoichiometry
O-5-1.6 V

potential.
theory

photo-response (1959).

formed

described

Gartner

The the

presence slow

of

localized and the

levels

acting

as traps dependence thickness. under the

was of

postulated the

in

order

to

explain The

response

potential of film

photocurrent. transitions with

spectral

response edge band

was independent eV were were

Indirect

an absorption No impurity

at 2.55 transitions

predominant found.

sub-bandgap

illumination.

Scherber tion
both

and Schroeder using tin

states, tinplate treated 6.4 V and a in

[ 1761 described Black

the

manufacture tin oxide,

for these and of A/dm2.

of in

solar which

energy the tin

absorpwas in

layers

oxide.

amorphous
the basis

oxidation Thus,

*constituted MS a

solarenergy degreased, 0.3, and

absorbent then it

surfaces. ws 0.3

mechanically solution density

cleaned

anodically mol/L at

consisting of 3.5

H3P04,

Na2HP04.12H20,

current

Leempoel, composed

et

al.

[ 1771 described

the with

behaviour

of

photo-electrochemical
coat ings.

cells

of Sn02

or Pt electrodes

phthal

ocyanine

37

(XII) This the

MISCELLANEOUS section of the are was tin compiles previous particular written

STUDIES studies sections, for by each Stirrup which yet are, they although are indirectly by related certain to one or

other

characterized

individual

trends A

which review of

study. and Hampson

[ 1781 on
were the

the

electrochemical

reactions

in aqueous

electrolytic

solutions. electrodes on Sn, and made Sn/SnS pulses. by Darwish, -et was of the The effect on the by higher the overthe

Electrochemical -al.

measurements SnS was during were the

on Sn/SnS

[ 1791.

The

electrodeposited rapid

electrode Values

anodically layer

polarized

galvanostatic from the on

rectangular observed

impedance of

calculated

resistance thickness of kinetics low the

overvoltage. revealed layer. were the Based determined cd. 2+ At through higher from

dependence of structural activation reaction cds, layer, voltages. kinetic the at

specific in the

impedance

the

layer

changes

semiconducting the

properties electrode at relatively the

overvoltage/cd the layer/solution

relations,

interface, step was more to the

values of

of Sn

rate-determining which

likely

diffusion of

a process

contributed values for

the rate

occurrence constants

appreciably calculated

Approximate parameters. of by the

were

Measurements Sn were hydrogen disk reported

hydride

hydrogen et of Ni, of al. anodic

overvoltage [ ISO]. The

on micro-electrodes anodic oxidation using a cell of

including hydride rotatingcurrent

Levinskas by of means Pt, Ag,

was studied

overvoltage

measurements and to Zn, with

microelectrodes mA.

Sn, Pb, amalgam, oxidation were

of < 0.2-0.3 mechanism:

The

kinetics

found

follow

a Volmer-Tafei

ZHH +

(A12H6).ether H + H2

Ze- + W

The

slow

step the

was

the

Volmer parameters

step.

Micro-electrode from

measurements Tafel

were curves. ions (it

used

to The high by ele-

determine exchange (order 3-4

kinetic

directly

experimental

current density in reactions involving negative hydrogen -6 of IO A/dm2), and was markedly sensitive to temperature in the range asymmetry of the silicate 21-33C), of the the and to the and hydride cathodic were oxide ion concentration

was changed

fold

in of

the

ctrolyte. tion

The

anodic

transition

energies

activa-

and the The

slowness of lead

Volmer

reaction of was tin

indicated electrode by

by the

measurements. in melts of

mechanism and

dissolution glasses

materials and

borosilicate

studied

Konovalov

Shashkin

[ 1811.

38

The

Moessbauer state

method of

in

absorption and the Sn02 glass. The melt by the

and

emission of

variants their of

was

used

to into

study

the

oxidation This and

Sn atoms that in

mechanism of

introduction alkali metal

glasses.

method Pb silicate

showed

interaction electrode The

melts

borosilicate into the

glasses of

with the

materials, of the

Sn was material played

introduced was

structural

network

dissolution

complicated role in

by electrochemical the interaction An

reactions. of the glass

submicron the

dissolution based Runge

no definite

with

material and

on Sn02. on the such the were the use of Z&n

investigation for

was the

made cathodic

Koeppen corrosion

[ 1821 of

electroplates being tration The suggested in most the

protection Factors from content a of

steel; affected

electroplates Zn concendiscussed. cd. Slight

as alternatives electroplate factors with

to during were alloys

tinplate. plating the Zn

which

stannate the bath

bath and

important was observed rapidly. At

corrosion decreased able ion

containing this

>, 4 % Zn, did

but not

the occur, and Cr

cathodic although corrosion and Cd

protection undesirprotectwere also

> 22 % Zn, were

phenomenon The best The effects

Zn corrosion were found

products with

formed. alloys.

durability of both

El % Zn

studied. Khmelevaya tion single ion the and of phenol crystal and Damaskin and aniline by [I831 reported the results electrode studying of the of a study the on the (001) adsorpof a

a polycrystalline with structure

and the

face of

Sn electrode. substances

In connection on the of the transition made by crystal n-electron from

dependence of

adsorpt-

of organic effect aniline

surface in the to

a Sn electrode, of phenol Sn poly-

was evaluated during The study the was

interaction a polycrystalline the

adsorption a single

crystal of

surface.

measuring

differential

capacitance

and single-crystal The effect Krstulovic corrosion polarization corrosion -i.e. high of

Sn electrodes Sn on the

(001). of of Al in natural alloys seawater (0.5-2-O was % Sn) investigated to prevent included determination of these by the the of alloys,

activity Use was in

and Karsulin of of rate steel the by in

[ 1843. seawater alloys loss.

Al-Sn

demonstrated. the same high that as medium, corrosion these

Measurements and the

AI-Sn weight

Relatively showed very

behaviour were anodes

corrosion that of steel dissolution alloys over

potentials, they were

alloys

electrochemically for the cathodic

active, protection The tin acid with anodic HCI

and

suitable

sacrifical

in seawater. and were electrochemical examined range Tests of of were the by characteristics Titova and of zinc base-tin [ 1851 in alloys alloys and

base-zinc medium the

Pecherskaya All in HCI was was process the

a sulphuric dissolved in in in the both HCI. were

a broad of H2 the

concentrations. also made

were Increase in tests that

evolution of

solutions. observed lower during

activity and H2S04,

metals the

Zn/Sn in the

alloys H2S04 anodic

although the

increase of

than

Factors

determining

intensity

dissolution

39

found

to be:

(i)

the of

anodic the

activity anions of

of the

the

surface

of The

the

alloys,

and ratio on the

(ii) of

the the

dissolution components

capability

media. was

quantitative to depend as on

participating of

in the anions

anodic

process

found as well

nature of

and concentration these components

in the

reactive

media,

the

contents

in the alloy. behaviour of [ 1861 for of dilute solutions and 0.80 of M SnBr2 KBr and PbBr2 in a

The nonpolar studied

electrochemical solvent by Elam,

consisting et al. peaks tetravalent

1.0 M AI2Br4 using the state cyclic

in ethyl-benzene Cyclic of the

was

voltammetry. and dissolution be

voltammograms divalent metal. range x lob6 had

showed well-defined Oxidation studied. cm/s little for to The the

deposition could were not

diffusion

coefficients the

detected in the potential -6 cm2/s for Pb and 2.7 1.1 x 10 of the Al, initial whereas

Sn, Pb ions inhibited An

electrodeposition associated with

Sn ions

or no effect. was

overvoltage for both 30 to

nucleation start

on a Pt until the

electrode overvoltage unstable

observed

metals. 40 mV.

Electrodeposition The formation potentials

did not of in

reached alloy

about at

thermodynamically solutions containing

Al/Pb

sufficiently

high cathodic

PbBr2 was indicated. Farr steel The and Saremi [ 1871 measured water. anion the potential were sweep curves (0.2 mV/s) Al, also for

in simulated effect

cooling

Measurements (MOO:-) inhibitor,

extended inhibitor the

to Cu, was

and Sn. studied.

of molybdate acted

as a corrosion provided that

Molybdate time

as an effective passivity. conductivity temperatures

surfaces

had adequate

to establish electrical

The reported

of

pure

ZnO

and

of

ZnO-doped [168].

with

SnO2

was

at different and

by Paria

and Maiti

Anodic Darwish Sn as well Sn were tion due at a of

cathodic

galvanostatic

polarization systems

experiments in alkaline 48.97

were

performed

by

and Fateen as three

[ 1891 on tin-selenium %-Se alloys: (I) 46.1

media.

Spec-pure (III) 97.0 polarizasurface achieved hydrogen %

% Sn, (II)

% Sn, and The activity was fall were HSnO; Cathodic _

used in 1.125 Sn and alloy

M NaOH (III) in to The

and 1.0 M Na2C03 I.125 form M NaOH HSnO; .

solutions. the

anodic of the

indicated Oxide

to a distinct relatively

tendency high cd.

formation a rapid

only in

cathodic

curves

revealed Alloys (I)

evolution, tally At

and the probable at a

formation low

of SnH4 cd (0.0.5

and (Ii)

also anodiand SeO3 polarizat-

dissolved high

relatively mA/cm*), evolution as alloy anodic

mA/cm) was

yielding attained.

cds (1.0-4.0 hydrogen

anodic

passivity

ion produced spec-pure basic 1.0 M

and the reduction (III) became was (II)

of Se to Se:with at a

In 1.0 M Na2C03, layer high cd of in

Sin as well when

covered performed gave

protecting

carbonate Na2CO3

polarization (I) and

a relatively the same

solution,

alloys

essentially

behaviour

characteristic

of each of them

in NaOH

solution.

40

Electrodeposition by Gunawardena C and SnO2 et

of Cd onto vitreous al. [198]. was The studied was

carbon

and tin oxide

electrodes

was reported vitreous influence was

eiectrochemical by the

nucleation

of Cd onto The

electrodes

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