British Corrosion Journal

ISSN: 0007-0599 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/ycst19

Review of inorganic coatings and coating

processes for reducing wear and corrosion

P.S. Sidky & M.G. Hocking

To cite this article: P.S. Sidky & M.G. Hocking (1999) Review of inorganic coatings and coating
processes for reducing wear and corrosion, British Corrosion Journal, 34:3, 171-183, DOI:
10.1179/000705999101500815

To link to this article: http://dx.doi.org/10.1179/000705999101500815

Published online: 18 Jul 2013.

Submit your article to this journal

Article views: 206

View related articles

Citing articles: 59 View citing articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ycst19

Download by: [UNAM Ciudad Universitaria] Date: 14 August 2017, At: 11:26
 Review of inorganic coatings and coating
processes for reducing wear and corrosion
P. S. SIDKY Advances in materials performance often require the development of composite systems, of
M. G. HOCKING which coated materials are one form. T he abrasion and corrosion resistance of components
can be greatly increased by protective coatings and this is a growing industry of considerable
economic importance. Coatings are used in both aqueous and high temperature applications.
Coal gasification, electric power generation, and waste incineration involve severe con-
ditions and thick coatings have proved eVective. Diesel and gas turbine engines are subject
to high temperature corrosion and highly beneficial coatings have been developed. Some
nuclear power systems also rely on coatings. Factors that must be taken into account include
substrate compatibility, adhesion, porosity, the possibility of repair or recoating, interdiVu-
sion, the eVect of thermal cycling, resistance to wear and corrosion, and cost. T his review of
alternative systems emphasises the necessity for the coating and substrate to be designed as
an integrated whole, bearing all of these considerations in mind.
Dr Sidky is with Corrosion and Materials Consultants L td, Suite 8, 25 L exham Gardens,
L ondon W 8 5JJ, UK. Dr Hocking is in the Materials Department, Imperial College,
L ondon SW 7 2BP, UK. Manuscript received 11 February 1998; accepted 21 May 1999.
© 1999 IoM Communications L td.
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017

INTRODUCTION The diffusion coatings successfully applied to early gas

Coatings provide a way of extending the limits of use of
materials at the upper end of their performance capabilities,
by allowing the mechanical properties of the substrate
materials to be maintained while protecting them against
wear or corrosion by applying a protective coating. A
comprehensive review on metallic and ceramic coatings,
containing over 2000 references, has been published as a
book1 which provides further information about each of
the subjects covered in the present paper.
The aim of the present review is to describe coating
systems and coating properties, including wear and erosion
resistance. The dependence of the properties of hard
coatings on the coating method and the corrosion resistance
of coatings are also discussed. Brief descriptions of the
coating processes are given, including one unusual but
simple and effective method (wire explosion coating).
Table 1 gives coating property requirements and Table 2
gives property and selection criteria for coatings in three
common areas of application (gas turbine, aerospace,
and nuclear).
METALLIC COATING SYSTEMS
Diffusion coating systems
Aluminising results in the formation of an alumina scale
producing surface which provides effective protection to
high velocity gas turbine blades, but a diffusion barrier
coating is also required. On steel, an aluminium coating
can be used at temperatures up to 500°C, above which
brittle intermetallics form.
Chromised steel (diffused in) is usable at up to 700°C
and this can be bent through 180° without damage.
However, at temperatures above 800°C, chromium diffuses
further into the steel, which impairs oxidation resistance
and leads to the formation of brittle intermetallics. This
effect can be offset by the addition of aluminium or silicon.
Chromium and titanium additions improve the resistance
to hot corrosion, and dispersed oxide particles, e.g. yttria
(Y O ), reduce spalling.
2 3
Aluminide coatings on superalloys lack ductility
and spall at temperatures below 750°C. To prevent this
the brittle b-NiAl or b-CoAl is embedded in a ductile c
solid solution matrix. The addition of yttrium improves
adherence.
turbine blades were linked to the substrate composition
and microstructure. A more recent improvement has been
the development of coatings which are much more
independent of the substrate. These are overlay coatings,
having less chromium and a higher refractory metal
content, with segregation as a consequence. Overlay
coatings are diffusion bonded to the substrate but without
the intention of converting the whole coating thickness to
NiAl or CoAl.
Overlay coatings
By the early 1980s, the most common method of coating
aerofoils was by electron beam evaporation and over
3 000 000 aerofoils worldwide had been successfully coated
by this method by 1982. The coatings used were of the
MCrAlY type (where M denotes nickel, cobalt, or iron,
alone or in combination). These alloys have a ductile
multiphase matrix (e.g. c-CoCr) with a high fraction of
brittle phase (e.g. b-CoAl). The presence of yttrium and
hafnium promotes the adherence of alumina during ther-
mal cycling.
Plasma sprayed coatings are porous; this reduces their
strength and decreases their corrosion resistance. Ion
implantation of aluminium in iron and of yttrium in Ni–Cr
and Fe–Ni–Cr alloys, etc. reduces oxidation. Yttrium also
improves scale adherence. Surface welded or clad systems
give good wear and corrosion resistance and are usually
over 3 mm in thickness. It has been found that multilayers
of hard alloys interleaved with ductile layers arrest cracks.
Rubbing seals are used in ceramic regenerators in gas
turbines, in compressors, etc., and require less than 25 mm
wear off per 100 h. The MCrAlY alloys, which are good
overlay coatings, have also made effective gas path rubbing
seals. At temperatures above 250°C, or in vacuum, fluid
lubricants are unsuitable so lubricating solids are used as
thin coatings in a binder. However, their adherence is poor.
Ion implantation is superior in this respect since the
additives are implanted directly into the substrate metal
without the problems associated with peelable coatings.
Also, no dimensional change occurs and no surface
roughening is necessary to provide a key for the coating.
Molybdenum and sulphur have been used successfully as
ion implants. However, whereas lead and silver perform
well under vacuum, they oxidise in air.2

ISSN 0007–0599 British Corrosion Journal 1999 Vol. 34 No. 3 171

 172 Sidky and Hocking Coatings for reducing wear and corrosion

A list of coatings that are suitable for use at high
temperatures is given in Table 3.
CERAMIC COATINGS
Ceramic coatings are used to provide protection against
corrosion by gases, molten metals, and solids and also as
thermal barriers against impinging flames and as radiative
heat reflectors; conversely, suitable ceramic coatings are
used to decrease heat losses from high temperature systems.
High temperature fretting and wear can be decreased by
the use of ceramic coatings.
Ceramic thermal barrier protection is required in vehicle
engines for piston crowns, cylinder shields and liners, etc.
A typical thermal barrier coating for gas turbines is a
plasma sprayed zirconia–7% yttria layer over a MCrAlY
(M=Ni, Co, or NiCo) bondcoat layer. The latter is plasma
sprayed at low pressure, which is essential for good adhesion.
Steel is coated for wear resistance with TiC and TiN
by activated reactive evaporation, reactive sputtering, or
chemical vapour deposition (see Ref. 1). The wear of TiC
coated stainless steel is improved by a factor of 34
compared with hard chromium plated material.
Ceramic coatings are usually thick and brittle. Also, they
devitrify, and may spall on thermal cycling. Nevertheless,
they give excellent resistance to oxidation and corrosion
and are very suitable for static components such as
combustion liners. However, further research is required
for application to rotating components. Examples of
ceramic coatings include complex silicates plus zirconia,
titania, alumina, ceria, etc., offering protection up to
1250°C. Nitrides may be incorporated to provide wear
resistance and to act as an effective thermal barrier, and
elements such as tin and aluminium may be added to
improve crack tolerance.
Vitreous enamel, silicides, and borides are used to protect
steels at temperatures of up to 600°C. Siliconising is used
for refractory metals because MoSi , WSi , and VSi have
2
good oxidation resistance. Another effective 2 coating method
2
used to apply chromium carbide on stainless steel for the
prevention of galling is the detonation gun method (see
‘Coating processes’ section below).3,4

Table 1 General property criteria for coating systems for elevated temperature service

Component system criterion/property Coating criterion/property

Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017

Aerodynamic property
Mechanical strength and microstructural stability
System adhesion, bonding and interface stability
Surface resistance to erosion and oxidation/hot
corrosion
Smooth surface finish for coating; must conform to appearance of precision
cast component
Coating must be resistant to all types of stress – impact, fatigue, creep, and
thermal – to which system will be exposed
Coating/substrate must be compatible without gross thermal or structural
mismatch; diffusion rates at interface must be at minimum at operating
temperatures, as must compositional changes; development of embrittling
phases must be avoided
Coating composition must have sufficient reserve of all reactant constituents
to meet scale reformation needs without marked deterioration in protection
ability; coating must be ductile, and must develop uniform, adherent, and
ductile scale at low rates

Table 2 Desirable properties of coatings and selection criteria

Applicable to

Property/criterion Gas turbine coatings Aerospace coatings Nuclear reactors

Adherent, crack and pore free Yes Yes Yes

Structure – non-columnar and defect Yes Yes Yes
tolerant
Microstructurally stable, precipitation Yes Yes Yes
strengthened, no brittle intermetallics
Thermal expansion compatible to Yes Yes Yes
substrate, resistance to thermal fatigue
Predictable reaction and interdiffusion with Yes Yes Yes
substrate which can be stopped or
manipulated to suit requirements
Coating should not affect mechanical and Yes Yes Yes
structural properties of substrate; should
improve bowing and cracking defects
Fatigue and creep resistant Yes Yes Yes
Resistant to brittle fracture, low Yes Yes Yes
ductile–brittle transition temperature
Isothermal and cyclic oxidation (aircraft) Yes Yes: hot corrosion not such a Yes: carburisation and
and hot corrosion (marine and industrial) threat hydrogen damage resistant;
resistant; impact and erosion resistant; hot corrosion not considered;
intergranular corrosion resistant; self- wear resistant and high
healing scratches and damages hardness coatings required
Spall resistant oxide scales; no molten Yes Yes Not applicable
reaction products; no vaporisation; have
thermal barrier effect
Locally repairable, applicable to partly Yes Yes: in situ repair difficult to No
corroded items and cost effective implement – otherwise repair
and cost effectiveness must
be considered
Low neutron capture No No Yes
Increased fuel life No No Yes
Drag sliding protection in Magnox reactors No No Yes

British Corrosion Journal 1999 Vol. 34 No. 3

 Sidky and Hocking Coatings for reducing wear and corrosion 173

Titanium carbide is used as a carbon diffusion barrier
for tantalum coatings on steel and TiN is used as a nitrogen
barrier on SiC heating elements.
Desirable properties for ceramic coatings
Elasticity is required to prevent spalling due to thermal
cycles. The elasticity of ceramics increases with porosity,
but open porosity allows corrosion and self-sealing ceramic
coatings have been developed with closed porosity.
A graded bond to the metal is essential and may be
obtained by continuous grading (e.g. during plasma spray-
ing) or by use of an appropriate bonding interlayer between
the alloy substrate and ceramic coating. Both CoCrAlY
and NiCrAlY can act as effective interlayers for ceramic
coatings such as calcium silicate. Glassy interlayers contain-
ing Si N and TiC have been used successfully for TiC and
3 4
TiN coatings on Si N tools.5
3 4
Chemical and thermomechanical effects can cause failure
of porous plasma sprayed zirconia–yttria, zirconia–
magnesia, and Ca SiO with NiCrAlY bond coat.
2 4
Degradation of thermal barrier coatings
Failure of thermal barrier coatings may occur owing to
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
(iii) ceramic barrier coatings – plasma sprayed stabilised
ZrO –Y O is highly recommended for internally
2 2 3
cooled components reaching very high outer surface
temperatures of the order of 1500°C.
COATING PROCESSES
Many coating processes are available, among which are
included: physical vapour deposition (PVD), evaporation,
reactive evaporation (RE), activated reactive evaporation
(ARE), biased activated reactive evaporation (BARE) or
reactive ion plating, sputtering, magnetron sputtering, rf
sputtering, reactive sputtering (RS), ion beam sputtering
(or sputter ion plating), ion implantation, chemical vapour
deposition (CVD), pack coating, vacuum pack coating,
pressure pulse pack coating, slurry coating, reaction sinter
coating, sol–gel coating, hot dip coating, electroplating,
electroless chemical coating, metalliding, laser coating,
rapid solidification coating, plasma spraying, detonation
gun (D-gun) coating, flame spraying, electric arc spraying,
wire explosion coating, liquid metal spraying, weld cladding
( hardfacing), rolling and extrusion cladding, explosive
cladding, electromagnetic impact bonding, diffusion bond-
ing, and hot isostatic pressing (HIP).
Processes may be categorised as follows:

poor bonding, coating porosity, microcracking, excessive

thickness, phase distribution, cohesive strength, thermal
expansion mismatch, residual stress of the coating–substrate
system, and bond coat failure. Thermal fatigue is also a
common cause of failure in ceramic coats.
Self-fluxing Ni–Cr–Si–B alloys have great resistance to
oxidation. They are arc sprayed from wire or powder; the
surface oxidation of the droplets, which would prevent
coalescence, is fluxed by the boron and silicon to give a
dense fused product, also cleaning the base metal.
A plasma sprayed MgO stabilised zirconia (MSZ)
thermal barrier coating over a mixed MSZ+NiAl coating
over a thin NiAl bond coat has been used in gas turbine
combustion chambers but oxidation of the NiAl occurs.
Superior bond coats are NiCrAlY and CoCrAlY, which
resist hot corrosion. The optimum ceramic overcoat on
Haynes 188 or Hastelloy X has proved to be an 8% yttria
stabilised zirconia.1 This did not peel or spall within
11 000 s in molten salt tests at 800°C or within 1000
thermal cycles from 400 to 900°C in burner rig tests.
Zirconia thermal barrier coatings can be surface sealed by
pulsed laser, giving smooth surfaces but with some cracks.
Burner rig tests of various types of high temperature
coating have allowed the following summary conclusions
to be drawn:1
(i) diffusion aluminides – high temperature/low activity
aluminides show adequate hot corrosion resistance
below 950°C for times up to 1200 h
(ii) MCrAlY overlay coatings – low pressure plasma
sprayed and physical vapour deposited coatings give
3–4 times longer life at temperatures up to 1050°C
(i) mechanical – cladding, bonding
(ii) physical – PVD, vacuum coating, thermal evapor-
ation, sputtering, ion plating, ion implantation
(iii) chemical – CVD, electroless plating
(iv) electrochemical – aqueous, molten salt
(v) spraying – detonation gun, electric arc, metallising,
plasma, flame (powder or wire)
(vi) welding – laser, manual metal arc (MMA), metal
inert gas (MIG), oxyacetylene, plasma transferred
arc, plasma welding, spray fusion, submerged arc,
tungsten inert gas (TIG) arc
(vii) hot dipping.
Physical vapour deposition
Physical vapour deposition includes three main techniques:
evaporation; sputtering; and ion plating. The steps in the
process may include:
(i) synthesis of the materials to be deposited, conversion
to vapour and, if a compound is to be deposited, a
vapour phase reaction to form it
(ii) transport of vapours to the substrate
(iii) condensation.
These steps can be independently controlled in PVD, which
is an advantage over CVD. Conventional PVD gives an
overlay coating, the purity, structure, and adhesion of
which can all be controlled.
Vacuum evaporation is much more rapid than vacuum
sputtering but coating composition and deposition rate can
be more readily controlled by sputtering. Ion plating gives
the strongest adhesion owing to its high deposition energy.

Table 3 High temperature substrates – types of coating

Substrates Coatings

Fe, Ni, Co base alloys Al, Cr, Si; MCrAlX (M=Fe and/or Ni and/or Co; X=Y, Hf, Ce, Zr, Ti, Ta, etc.)
with variations
Cermets: Co–Cr C ; Ni and/or Co with ceramics – Al O
2 3 2 3
Ceramics: various oxides, carbides, borides, and nitrides
Platinides: other refractory metal depositions
Refractory metals: Nb, Ta, W, Mo, Cr Silicide coatings: Si–(Mo, Nb, Cr–Ti, Al–Cr) with Al, B, Cr, Ti, and V additions
Aluminide coatings: Al–(Nb, Ta, Ni) with Cr, Si, Sn, and Ti additions
Beryllide coatings: Be–(Ta, Ti, Nb, Cr, Mo, Zr)
Others: Nb–Zn
Graphites Ir, SiC
Oxides: HfO , ThO , ZrO
2 2 2
Borides: HfB , ZrB
2 2

British Corrosion Journal 1999 Vol. 34 No. 3

 174 Sidky and Hocking Coatings for reducing wear and corrosion
PEB: primary electron beam
1 Schematic diagram of activated reactive evaporation
equipment
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
The advantages of PVD over other overlay coatings such
as electrodeposition, CVD, and plasma spray are:
(i) great versatility in deposit composition – almost
any alloy or refractory and some polymers can be
deposited
(ii) substrate temperature can be varied over a wide
range
(iii) vapoforms can be produced at high rates
(iv) very high purity deposits can be formed
(v) excellent bonding to the substrate is possible
(vi) excellent surface finish can be achieved
(vii) thicknesses of up to 250 mm are attainable.
Drawbacks are that PVD is mainly restricted to line of
sight deposition; the throwing power can be poor and the
equipment is expensive.
Evaporation
Physical vapour deposition processes usually operate at
working pressures in the range 10−3–1 mbar. Nucleation
and growth kinetics govern the development and micro-
structure of the coating. Evaporation usually involves
resistance heating from a foil or boat of tungsten,
molybdenum, or tantalum or, if these react with the liquid
pool, a refractory boat can be used (e.g. BN–TiB , which
2 float glass substrate at room temperature.
is electrically conducting, is used for aluminium). Other
heating methods include electron beam heating by ther-
mionic gun or plasma gun.
In the thermionic gun process, electrons emitted from a
hot cathode are attracted towards an anode at 10–40 kV
at 10−5 mbar (negligible ionisation). The anode is the
evaporant.
Using the plasma electron beam gun, an electric field
applied to a low pressure gas generates electrons. The large
number of ions also present cause high coating adhesion.
Many designs give improved performance. Coatings of
CoCrAlYTa and NiCrAlYSi applied by electron beam
PVD are more protective than the plasma sprayed versions,
but a high vacuum is necessary, in contrast to sputtering.
A deposition rate of 25 mm min−1 is possible but deposition
is limited to line of sight. Millions of aero gas turbine
blades have been coated in this manner.
Reactive evaporation involves the evaporation of a metal
or its compound in the presence of some reactive gas to
form a compound, e.g. silicon or SiO in oxygen to form a
silica coating or titanium in nitrogen to form a TiN
2
British Corrosion Journal 1999 Vol. 34 No. 3
2 Schematic diagram of sputter coater
coating. The mean free path is greater than the source to
substrate distance and so reaction only occurs on the
substrate (in contrast with CVD).
Activated reactive evaporation (see Fig. 1) is similar but
at a slightly higher pressure and with the mean free path
less than the source to substrate distance so that the
reaction occurs in the gas phase before deposition occurs
(as with CVD). This allows stoichiometry variation, e.g. of
TiC coatings.
In BARE, also termed reactive ion plating, the substrate
is negatively biased to attract the positive ions in the
plasma. Other variants are also in use.
Sputtering
Sputtering (see Fig. 2) is a momentum transfer process in
which a fast ion (e.g. Ar+) collides with an atom from a
cathodic surface and sputters it out towards a substrate.
Sputtered films have compressive stress whereas evaporated
films have a tensile stress. Low stress is conducive to
adhesion but compressive stress may reduce cracking.
Carbon with a diamond structure has been sputtered
onto steel.
Magnetron sputtering creates fields which cause the
electrons (emitted from the cathode) to follow long helical
paths which result in many more collisions with the argon
gas atoms and so generate many more Ar+ ions for
sputtering. Scale-up allows inside coating of 2 m length
steel tubes.
Many improved magnetron sputtering processes have
been devised. The substrate is cleaned by ionic bombard-
ment before the sputtering. Adherent dense coatings can be
obtained at lower substrate temperatures than by CVD.
Type 304 stainless steel has even been sputtered onto a
Chromium, magnetron sputtered in argon containing
methane or nitrogen at 2×10−3 mbar pressure, has a
hardness of up to 3500 HV, with fretting, wear, fatigue,
and corrosion resistance superior to those of electrolytic
hard chromium plate. Also, highly corrosion resistant films
of amorphous Co Nb , Fe Cr P C , Cr B , and
100−x x 80−x x 13 7 75 25
Ti B alloys have been sputtered onto water cooled
25 25
copper substrates.
Radio frequency sputtering can be used for insulators
(which are unable to be dc sputtered because they become
charged). Electrons in the plasma prevent charging and ion
plating then occurs in the appropriate half cycles.
Reactive sputtering occurs when one of the species is
gaseous, e.g. sputtering aluminium in oxygen to form
alumina coatings, titanium to form TiN, and niobium to
form NbN.
Ion plating
Ion plating (or ion beam sputtering) allows independent
control of the energy and current density of the bombarding
 Sidky and Hocking Coatings for reducing wear and corrosion
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
3 Schematic diagram of ion plating
ions. A vacuum chamber (10−5 bar) at 300°C is lined with
coating source plates at −1 kV (which causes ion bombard-
ment and the consequent sputtering of material from them).
The coating substrates are held at −100 V (to ion polish
them without significant resputtering). No manipulation of
the specimens is necessary because there is good throwing
power (Fig. 3).
Electroplated cadmium can be replaced to advantage by
ion vapour deposited aluminium (cadmium on strong
aluminium and steel alloys promotes exfoliation corrosion).
Aluminium coatings are usable at up to 500°C. However,
coating structure and stress are affected by substrate bias.
Ion plating with aluminium to protect uranium from
oxidation has been successful, in contrast to ordinary
vacuum evaporation, which is hindered by a thin UO film
2
which forms immediately on uranium on cleaning. In argon
glow discharge ion plating, the specimen (uranium) surface
is sputter cleaned by Ar+ ion bombardment and is then
held contamination free until (and during) the ion plating
process. The high energy Ar+ collision with the surface
heats it and promotes diffusion. The maximum substrate
diameter is 25 cm at present. Ion plating is suitable for
wear and erosion resistant coatings owing to its strong
adhesion (e.g. HfN for low friction, and TiC for deformation
resistance and good bonding). For an incompatible sub-
strate and coating, ion plating can be used as a ‘strike’ for
electroplating.
The advantages of ion plating include strong adhesion
at low substrate temperatures, effective coverage of complex
shapes, and desirable structures and structure dependent
properties at low substrate temperatures.
The disadvantages of ion plating are that specimens
must be fixed to a high voltage electrode, relatively high
gas pressures must be used, which is problematic, and
deposition energies lie in a wide range and are difficult
to control.
Ion implantation
In ion implantation, selected atomic species are ionised
then accelerated in an electric field to between 10 and
1000 keV in a vacuum of 10−5 mbar. The ion source and
extraction electrodes are designed such that the ions emerge
as a beam. Ion penetration is only to about 0·2 mm but the
material properties are greatly altered.
175
(a) (b)
1 temperature monitor; 2 heating elements; 3 substrates; 4 inlet;
5 exhaust
4 Schematic diagrams of experimental chemical vapour
deposition apparatus using a resistive and b induction
heating
Advantages of ion implantation are that high temper-
atures are not required, so no thermal distortions of the
substrate occur. Also, the absence of any interface eliminates
coating adhesion problems. Furthermore, surface finish is
improved as sputtering produces a polishing effect. The
implanted species is finely dispersed, which improves its
effect during corrosion, and biaxial compressive stress is
induced in the surface, which closes surface microcracks in
ceramics. In metals these stresses can be annealed out.
Chemical vapour deposition
Chemical vapour deposition (Fig. 4) involves the deposition
of elements and compounds from a reaction in the vapour
state, with good throwing power. Coating thicknesses are
from 5 to 250 mm. In this process a solid reaction product
nucleates and grows on a substrate as a result of a gas
phase reaction. Heat, plasma, or ultraviolet light can enable
it. Similarly to electroforms, thick free standing vapoforms
can be produced, e.g. from tungsten and W–Re in complex
shapes. Many factors affect the quality of a CVD coating,
such as gas reactant composition, flowrate, Reynolds
number, substrate temperature, and total gas pressure. In
consequence, many manufacturers do not disclose the
optimum parameters.
Typical CVD coatings include boron, carbon, niobium,
silicon, tantalum, tungsten, AlN, BP, BN, IrO , RuO , SiC,
2 2
Si N , SiO , TiB, TiC, TiN, TiCN, ZrN, ZrSi , ZrC, B C,
3 4 2 2 4
chromium carbides, (Fe,Mn) C, HfC, Mo C, NbC, TaC,
3 2
TiC, VC, W C, ZrC, CrN, Fe N, HfN, NbN, Ta N,
2 4 x
alumina, chromia, hafnia, niobia, titania, yttria, Fe O ,
2 3
In O , SnO , Ta O , V O , MoB, NbB , TaB , TiB ,
2 3 2 2 5 2 3 2 2 2
and WB.
Substrates include titanium, tantalum, molybdenum,
tungsten, carbon, platinum, iron, nickel, cobalt, superalloys,
Inconel, SiO , SiC, ceramics, glasses, BN, cemented car-
2
bides, copper, silicon, niobium, etc.
Possible adverse effects on a substrate of the high
temperatures encountered in CVD may be avoidable by
applying plasma technology. Laser assisted CVD and metal
organic CVD are also important methods. Some substrate–
deposit reaction is expected, which may be beneficial
for bonding.
Usually a CVD reactor has a cold wall and only the
substrate is heated so that deposition does not occur on
the walls.
Substrate preparation, heating, and positioning are
important factors. Turbulent gas flow is to be avoided for
British Corrosion Journal 1999 Vol. 34 No. 3
 176 Sidky and Hocking Coatings for reducing wear and corrosion
1 stainless steel; 2 molybdenum can; 3 pack mixture; 4 fusible
silicate
pack material: alumina–3Cr–11Si–0·25 ammonium iodide (wt-%)
5 Schematic diagram of pack (diffusion) coating of non-
ferrous metals
several reasons including its uncontrollable local cooling
effects.
The thermodynamic theory of CVD is well understood
but the kinetics involve many factors and prediction of the
overall process is difficult.
Some advantages of CVD are that: it is versatile and can
produce some coatings that would not otherwise be readily
obtainable; it can be applied to powders (in fluidised
bed reactors), wires, wafers, and complex shapes; it is not
restricted to line of sight situations; it uses relatively simple
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
equipment; deposition is possible over a wide range of
pressure and temperature; there is a range of available
chemical systems/reactions, so that (for example) hydrogen
embrittlement can be avoided; it has good throwing power;
composition can be controlled to give graded coatings; the
coating structure and grain size can be controlled; and
uniform coating is possible even on complex shapes.
The disadvantages of CVD are that it operates at a
higher temperature than PVD (1000°C as opposed to
500°C) and so substrate overheating is possible. Undesirable
directional deposits are also possible.
Pack coatings
Pack coatings are available in several variants, including
vacuum pack, slip pack, pressure pulse pack, etc. The pack
can be all solid, or part fluid (slip pack). The technique is
a special type of CVD where the substrate is buried in a
mass of the depositing medium, which is a mixture of the
master alloy with a salt activator. This pack is then heated
at pressures that can vary from 1 mbar to 1 bar. It is a
convenient process for gas turbine blades and rocket/
spacecraft hardware. Large items can be coated as well as
intricate shapes. The most common coatings are alumin-
ium and chromium (see Fig. 5). During pack aluminising
of nickel superalloy turbine blades, Ni Al and other
2 3
intermetallic phases are formed. Good protection against
superalloy hot corrosion is provided by a duplex silicon
slurry and aluminide formed by a slurry or a spray of pure
silicon followed by a 16 h pack aluminising treatment
at 1100°C. Steel can be pack boronised for wear resistance,
giving well bonded layers of FeB+FeB .
2 and thermal cycle resistant coatings.
Duplex Pt–Al can be pack coated onto nickel base
superalloys to give improved ductile to brittle transition
temperatures. Pack chromising of steel uses typically
50%Cr powder, 1%NH Cl, and 49% alumina (as an inert
4
filler to prevent excessively rapid coating). This gives
30–45%Cr in the surface.
Advantages of pack coatings are good uniformity at low
cost, with good dimensional tolerance. Hard deposits,
5–80 mm in thickness, can be produced but substrate size
is a limitation and the technique is not suitable for high
temperature sensitive substrates. Thinner coatings are
obtained than from other diffusion processes and embrittle-
ment is possible.
Vacuum pack processes require no inert filler. The
pressure pulse pack process involves evacuation and
refilling of the system about eight times per minute at
British Corrosion Journal 1999 Vol. 34 No. 3
900°C. It is especially suitable for coating crevices such as
the cooling channels of gas turbine blades.
Slurry coating uses a finer mesh metal mixture than pack
coating and is carried out at a temperature above the
melting point of the mixture.
The reaction sinter coating process is an extension of
slurry coating, designed to prevent the total loss of deposit
identity which occurs in the diffusion process.
Sol–gel coating
Sol–gel coating is probably the most economical process
for producing high temperature ceramic coatings. The meth-
od involves four stages: (i) sol preparation; (ii) spraying
sol onto the substrate; (iii) drying the sol to a gel; and
(iv) firing to obtain a coating.
Colloidal dispersion preparations are well characterised
and can be aquasols or organosols, aggregate or non-
aggregate in nature. They are stable dispersions of particles
in a fluid of colloidal units of hydrous oxides or hydroxides
with particles having sizes of 2 nm to 1 mm.
Sol preparation is either by hydrolysis followed by
polymerisation, or by precipitation and then peptisation.
Only oxides have been sol–gel coated so far, but sol–gel
coating of nitrides may also be possible.
Sols are applied by immersion, spinning, electrophoresis,
or spraying. The sol to gel transformation is carried out by
slow drying then firing at 500–1200°C for 15 min. A single
such application gives a 0·1 to 2 mm thickness coating.
Unlike slurry coats, there may not be a distinct diffusion
zone, but the coating oxide and a growing oxide are
interspersed. Sol–gel coatings have been characterised as
beneficial for oxidation resistance.
Hot dip coating
Hot dip coatings are traditionally applied to ferrous alloys.
A metal such as zinc, aluminium, tin, or lead is vat melted
and the object to be coated is passed through. Precleaning
of the substrate involves the use of hot reducing gas
(N +H at 800°C) as the final stage following the
2 2
conventional steel cleaning steps.
The thermal cycling during hot dipping of steel in
aluminium renders it less ductile but stronger. Brittle Fe Al
3
forms and should be less than 10 mm in thickness if ductility
is required.
Relatively thick coatings may be obtained by hot dipping
which is a rapid coating method, giving coatings that are
typically 25–130 mm in thickness.
Hot dipping to provide a thermal barrier coating may
be undertaken in a Zr–25 wt-%Ni eutectic with 5 wt-%Y
as a stabiliser for the zirconia to be formed in the final
conversion step. Superalloys have been dipped at 1030°C
for 1 min in argon, then annealed for 4 h, and finally held
in a partial pressure of oxygen of 10−17 bar (using an
H O–H –Ar mixture) to convert selectively to zirconia
2 2
(without oxidising the nickel or cobalt), giving adherent
Electroplating and chemical coating
Aqueous electroplating is cost effective. Fused salt electro-
chemical coating yields precious metal and refractory
deposits, including cermets, but molten salt methods require
rigorous control to prevent ingress of water vapour and
oxidation.
Coating thicknesses of 0·25 to 250 mm can be applied.
However, good plant design is necessary for maximum
throwing power.
Surface preparation before coating is essential and
etching to a depth of 0·1 mm is necessary for strong
adhesion. The electrolyte condition is an important para-
meter and has been well characterised in standard texts.
Composites such as cermets can be electrodeposited by

(a) (b)
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
(c)
a simple cell with air agitation and slurry circulation; b tank with
plate pump and slurry circulation; c triple cell arrangement in series
and solution flow in parallel
6 Schematic diagram of electroplating with
composites
loading refractory powders or fibres into the electrolyte
and ensuring that it is well stirred. Electrodeposition of
overlay coatings is a simpler process than PVD or CVD
but, because the deposition is a low energy (ambient
temperature) process, adhesion may not be as strong unless
suitable heat treatment is undertaken.
Barrel plating for co-depositing 10 mm MCrAlY powder
in a cobalt or nickel matrix has been used for gas
turbine blades.
Electrophoretic composite coatings require fine particles
in a liquid dielectric which migrate in an electric field and
deposit on an electrode. High rates (1 mm s−1) are possible,
with good thickness control and throwing power, but heat
treatment is essential to sinter and densify (see Fig. 6).
The main drawback of electroplating is the necessity to
achieve adequate throwing power. Furthermore, interlayers
may be required. Factors to be taken into account are:
substrate–coating bonding, e.g. for substrates of stainless
steel, aluminium, tungsten, niobium, molybdenum alloys,
etc. a copper strike that would be suitable for low
temperature use will be unsuitable at high temperature; the
possibility of substrate oxidation in the aqueous electrolyte;
and the risk of the in situ incorporation of sulphur,
phosphorus, hydrogen, or other undesirable radicals in the
electroplate. In addition, coatings may be porous and
stressed, exacerbating such problems.
Electroless coating
Also known as chemical coating, this is a cold coating
technique (non-electrolytic), e.g. for nickel, and has good
throwing power giving very uniform coatings (unlike
electroplating) on complex shapes and large components.
It also gives a quasicrystalline or near amorphous deposit.
Sidky and Hocking Coatings for reducing wear and corrosion 177
1 defocused laser beam; 2 water cooled, reflector copper dome;
3 powder feed hopper; 4 argon propellant gas; 5 25 kHz ultrasonic
vibrators set in rubber and housed in steel box; 6 ultrasonic
amplifier; 7 to ac supply; 8 hydraulic controlled x–y table, x direction
is melt bead running line, and y direction is shift for overlapping
laser tracks
7 Schematic diagram of laser coating
Electroless nickel contains 7–10%P, but has high corrosion
and wear resistance and low porosity.
Metalliding
Metalliding (or fused salt electroplating) can be used for
the diffusion coating of iron, nickel, cobalt, molybdenum,
tungsten, niobium, titanium, chromium, etc. with beryllium,
boron, aluminium, silicon, titanium, vanadium, chromium,
manganese, yttrium, zirconium, and rare earths, in fused
fluorides or chlorides. Metalliding is of interest for surface
hardening and for corrosion protection. For example,
molybdenum burns away in air at 650°C but withstands
1300°C for several hours if it is silicided.
cermets/ Laser coating
A pure iron surface can be precoated with DAG graphite
and then laser surface melted for (e.g.) 12 times, reapplying
graphite between each melting. In this manner, up to 6%C
can be alloyed into the surface to carburise it.
Silica coatings have been laser fused onto Incoloy 800H
and dense zirconia layers have been deposited by pulsed
laser. Laser cladding of triballoy, nickel alloys, WC+Fe,
TiC, silicon, and alumina can be achieved by flame spraying
followed by laser surface melting. Plasma sprayed porous
coatings can be laser surface melted (without melting down
to the interface) to seal surface porosity but without
removing bulk porosity (which confers some elasticity to
ceramics). Mild steel has been laser clad with stainless steel
(see Fig. 7). Powdered coating material can be blown onto
a substrate by argon, while applying a laser beam. The
beam melts the powder which then falls onto the surface,
protected by an argon envelope.
Rapid solidification processing
Rapid solidification processing can be achieved by having
a very large temperature difference between the substrate
and coating (originally in powder form, or from another
type of coating method such as PVD). The coating is thus
made amorphous.1
Metal spraying
Thick uniform coatings can be obtained by metal spraying.
However, the success of the process is dependent upon the
skill of the operator. Substrates must be heat tolerant
except in plasma and wire explosion spraying. Disadvan-
tages are that porous and rough coatings may be produced.
Plasma spraying
This uses an inert gas stream to carry powder into an
atmospheric pressure or low pressure plasma. Any required
British Corrosion Journal 1999 Vol. 34 No. 3
 178 Sidky and Hocking Coatings for reducing wear and corrosion
1 water cooled anode; 2 gas stream; 3 centre cathode; 4 plasma
stream carrying injected powder via carrier gas; 5 alternative powder
injection locations; 6 substrate; 7 coating
interacting parameters influencing plasma coating: plasma torch –
relative movement of torch and torch–substrate distance; plasma –
gas composition, heat content, temperature, air dilution, and velocity
of plasma stream; powder – particle shape, size distribution, and
individual constituent composition within particles, dwell time in
plasma stream; substrate – temperature, initial and during coating,
residual stress effects, quenching rates of incident coating material
8 Schematic diagram of plasma coating torch and substrate
coating thickness may be achieved but problems that
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
may be encountered include porosity and poor adhesion,
especially of ceramics to metals. Adhesion is improved if a
bond coat interlayer is used (e.g. Ni–Al or molybdenum)
and/or if powder with a small particle size is used
(see Fig. 8).
Plasma torches use water cooled copper anodes and
tungsten cathodes. A mixture of argon and hydrogen flows
around the cathode at 3·5 L min−1 and exits through the
anode nozzle. A dc arc is maintained and the plasma of
ions and atoms emerges at a temperature of 6000–12 000°C
at a distance of 1 cm from the nozzle, decreasing rapidly
to 3000°C at a distance of 10 cm from the nozzle. Near the
nozzle, the gas velocity is 200–600 m s−1 but the particle
velocity is only 20 m s−1. However, the particle acceleration
(due to gas frictional forces) is 100 000g so that 18 mm
particles reach a maximum velocity of 275 m s−1 at a
distance of 6 cm from the nozzle. The very high temperature
melts even the most refractory particles but low melting
point materials such as plastics can also be sprayed. The
plasma jet is typically 5 cm in length and distance from the
substrate is of the order of 15 cm. A power of about 80 kW
(typically 700 A) is required. Oxidation is minimal because
of the low dwell time and the use of a reducing gas. The
substrate rarely exceeds a temperature of 320°C and is
often below 150°C. Plasma spraying is the type of spraying
process which causes no distortion of the substrate.
For strong dense plasma sprayed coatings, most of the
particles must be molten before impingement and must
have sufficient velocity to splat into the irregularities of the
previous splats. Many coatings contain readily oxidised
elements (e.g. aluminium, molybdenum, and titanium) for
which plasma spraying at low pressure (20 mbar) or in
argon is advantageous. Underwater plasma spraying offers
much scope for deposition of wear and corrosion resistant
coatings on submerged substrates such as offshore struc-
tures, e.g. with powders of the self-fluxing nickel based
hardfacing alloys Colomonoy 5, 52, and 42 containing the
metalloids boron and silicon to reduce oxide films on
the base metal. Coatings with thicknesses in the range
100–300 mm have been deposited in this manner.
L ow pressure and vacuum plasma spraying
These methods are used for metals that are too reactive to
be sprayed in air. The increased particle velocity results in
high quality pure coatings. The jet velocity is Mach 3,
giving low porosity and strong adhesion. However, the
equipment used is expensive.
British Corrosion Journal 1999 Vol. 34 No. 3
1 dc power source, 30 V, 300 A; 2 wire feed – drive and reel; 3 wire;
4 arc; 5 substrate
9 Schematic diagram of electric arc spraying
Detonation gun coating
Known as D-gun coating, this technique explosively propels
molten powder particles onto the substrate. A D-gun is
typically a water cooled barrel about 1 m in length with an
internal diameter of 2·5 cm, into which is injected a powder
(the coating material ) and a mixture of oxygen plus
acetylene which is repeatedly exploded at a rate of 4–8
detonations per second by a spark plug. The explosions
accelerate the powder to about 700 m s−1 (a much greater
velocity than in plasma spraying) and cause it to melt (at
4200°C), so that it splats rapidly onto the substrate.
Advantages of D-gun coating are that relatively simple
equipment is used to produce coatings of low porosity and
high bond strength which are tolerant of impurities.
Substrate pretreatment is not stringent yet strong bonds
are produced with only moderate substrate heating during
deposition, which occurs at a high coating rate.
All plasma and D-gun coatings have some open porosity
which may allow corrosion, especially by molten salts. The
porosity can be reduced by sintering or other methods
(see below).
Flame spraying
This technique involves 25 times less kinetic energy than
D-gun coating but is adequate for some purposes, e.g. for
the production of thermal barrier coatings on rocket
nozzles and jet engine combusion chambers. A wire or
powder feed of the coating material is fed into a flame,
melts, and is blown onto the substrate by a rapid
compressed air blast. Applications include: protecting
against corrosion at ambient and high temperatures;
rebuilding worn parts; and providing wear, erosion, and
abrasion resistance. Coating materials vary from aluminium
to alumina. Porosity is much greater than for D-gun
coatings. The spray may contain many non-molten particles,
depending on the melting point of the feed. Porosity can
be reduced subsequently by resin vacuum impregnating or
by laser surface melting.
Electric arc spraying
This method uses two feedable wires as the electrodes for
a dc arc and the resulting molten droplets are blown onto
the substrate by a compressed air blast (see Fig. 9). The
molten drops are coarser but hotter than those from flame
spraying and their adhesion is stronger. Pseudoalloy
coatings may be obtained by feeding different wires through
each electrode. Thus, a two phase alloy of copper and
stainless steel can be produced, giving high wear resistance
due to the steel and high thermal conduction due to
the copper.
L iquid metal spraying
Using the Osprey metal spray process, this technique can
build up very thick (e.g. 5 cm) metal coatings very rapidly
(within minutes). The coating metal is induction melted
and atomised by an annular blast of inert gas at the bottom
of the melt crucible as it emerges through a hole into a
reduced pressure area containing the substrate.
 Sidky and Hocking Coatings for reducing wear and corrosion
Coating by welding
(hardfacing, weld cladding)
Properties of hardfacing alloys are reported elsewhere.1
The weld coating methods used for the production of
hardfacings include gas, powder, MMA, MIG, TIG (which
includes plasma arc), submerged metal arc (SMAW), and
friction welding. These methods produce coatings which
resist heavy wear under conditions of mechanical and
thermal shock. Generally, ferrous alloys are used for
abrasion resistance, nickel and cobalt alloys for oxidation
and corrosion resistance, copper alloys for bearings, and
WC, CrB, etc. for wear resistance. The main concern is the
dilution of the coating which occurs as some of the
substrate melts into it. This can be controlled to as low as
5%. Cracking of thick layers can be minimised by apply-
ing an intermediate soft metal layer and by preheating,
especially when brittle and hard alloys are deposited.
Other cladding processes include: explosive impact
cladding; magnetic impact bonding; HIP; and coextrusion.
Cladding and bonding can give very thick coatings on
large substrates, but substrate distortion is possible; these
processes are particularly suitable for robust substrates.
Rolling and extrusion processes have been used in
coating many ferrous alloys, Ni–Fe alloys, aluminium
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
alloys, etc. to provide resistance to corrosion and oxidation
for ambient and high temperature applications in sulphur
and chlorine containing environments and for other high
temperature applications in the energy, aviation, and
nuclear industries. Type 310 stainless steel coextruded with
50Ni–50Cr alloy has given very good service under hot
corrosion conditions in boiler systems. A thin electrodepos-
ited interlayer usually gives a superior bond for clad creep
resistant steels.
Explosive cladding can be used to form multilayer
laminates of identical alloy sheets such as Al–Li which are
impossible to bond by diffusion bonding.
Diffusion bonding
Many coating processes include heat treatment as a step
to ensure strong bonding. However, diffusion bonding
can be used as the primary bonding process. In diffusion
bonding, the components are pressed together and heated
to cause interdiffusion, a slow process. Composition,
microstructure, and physical, chemical, and mechanical
properties are affected and controlled by the time and
temperature of heat treatment, the pressure, and the cooling
rate. The temperature should be 0·5–0·8 of the absolute
melting point (in K). Additional layers of coatings a few
micrometres in thickness, or loose shims, are interposed
either to promote bonding or to act as diffusion barriers
to specific elements.
Some of the disadvantages of diffusion bonding include:
poor adherence over large areas due to impurities such as
oxides or grit at the interface; poor bonding due to interface
separation via vacancy concentration and void formation
during diffusion; and unknown thermal effects on the
properties of the bonding elements.
Aluminising and chromising on steels and nickel alloys
have been industrial diffusion bonding techniques for
decades. Two problems which must be overcome for
effective bonding of aluminium on steel are the oxide,
which forms readily on aluminium, and brittle intermetallics
(e.g. FeAl ) which form at the interface. Several remedies
3
are available.
Hot isostatic pressing
Hot isostatic pressing is a fairly new process and is suitable
for complex shapes. Gas turbine alloys have been clad with
the MCrAlY series of coatings by HIP and metals clad
with ceramic coating systems have also been produced. The
coating material is positioned by spot welding or powder
179
spraying and is then enclosed in a flexible membrane (e.g.
glass chips, which subsequently melt) within a deformable
metal container. The HIP is then undertaken at high
temperature and pressure and diffusion bonding occurs.
Electromagnetic impact bonding
Electromagnetic impact bonding uses magnetic energy to
provide the impact, causing cladding to take place in a
similar manner to the chemical explosion method. In a
few microseconds a pressure of 300 MPa can develop. The
bonding can be carried out either hot or cold. However, it
is limited to circumferentially continuous objects such as
tubes and rings. It has also been used for gas turbine blades.
Wire explosion coating
Wire explosion coating is a simple but relatively little
known process, first used by Faraday in the nineteenth
century, which gives excellent coatings.
The internal coating of tubes in air at atmospheric
pressure is readily accomplished by wire explosion spraying.
If a wire is exploded electrically by passing a very high
current through it, a shower of very fine droplets can be
produced, travelling at 600 m s−1 (>2000 km h−1).
Typically, a bank of capacitors charged to 15 kV is
discharged across the ends of a wire, instantaneously
producing about 1011 W of power (which is more than the
entire UK national grid generating at full load), producing
a temperature >106 K. The surface of the wire heats up
and vaporises before its centre, owing to the rf ‘skin effect’
and the magnetic ‘pinch effect’ which is a consequence of
the very high concentric magnetic field generated by the
enormous current in the wire. This exerts a very high
inward radial pressure on the wire (pinch effect), confining
it and preventing an early explosion. For example, calcu-
lation shows that a 25 mm wire carrying 105 A experiences
107 atm pressure on its surface (far higher than the boiling
pressure).
The wire first develops a liquid surface layer around the
unmelted core. Vaporisation can only occur at the wire
surface, which must vaporise first. A rarefaction front thus
moves in at the speed of sound from the surface to the core
(although electrical heat enters even more rapidly). Initially,
the magnetic pinch effect prevents the escape of any vapour
from the surface. However, when the whole wire becomes
molten, surface tension causes droplets to start forming
along its length, joined by narrow necks. Greater magnetic
pinch force occurs at positions of reduced radius, which
enhances the formation of discrete droplets. Once the
droplets become separated, the current ceases and so does
the pinch effect. The unconfined wire then explodes and is
transformed into a plasma expanding at over 2000 km h−1.
This unusually high velocity gives the resulting spray of
metal droplets, which are typically 2–3 mm in diameter, a
high impact energy on the surface being coated, resulting
in excellent adhesion. Because the thermal capacity of the
plasma is low even paper can be coated.
About 60% of the wire mass can be deposited onto the
bore of a cylinder if an axially located wire is exploded
within it. This method is currently being used to coat the
aluminium alloy cylinder bores of diesel engines with
molybdenum. The explosion of a single wire results in a
coating thickness of 5–15 mm and any required final
thickness can be achieved by repeating the process.
Coating by wire explosion can be undertaken in air at
atmospheric pressure. The wire vapour reaches the substrate
first, which excludes air and prevents oxidation of the
shower of molten droplets which follows. The layer formed
is smoother, denser and more adherent than those produced
by either plasma or flame spraying and possesses high wear
resistance and low friction. Coatings of molybdenum,
tungsten, and piano wire on aluminium or steel have 5
British Corrosion Journal 1999 Vol. 34 No. 3
 180 Sidky and Hocking Coatings for reducing wear and corrosion
times stronger adhesion than can be achieved by flame
spraying. All metals can be applied in this way if available
as wire of diameter 10–1500 mm. Any object can be coated,
including those made from paper, metals, ceramics, and
glass. A modification of the technique can be used to join
flat ceramic surfaces together, by exploding tantalum foil,
and copper can be joined to silicon in the same manner.
Typical equipment requirements for wire explosion
coating include a 20 kV dc power supply unit and a 20 mF
low inductance capacitor bank. The optimum wire diameter
for maximum shock wave energy (which gives greatest
adhesion) is about 0·5 mm for a power input of 500 J cm−1
( less for smaller energies). Further increase of stored energy
has little effect.
Very thin wires explode too rapidly, using little of the
available energy in the capacitor bank. Thick wires absorb
insufficient energy to vaporise them (even if there is enough
stored energy in the capacitors to vaporise the wire
completely).
A foil supported on the inside of a perspex cylinder will
explode only inwards and will thus coat the exterior of a
tube placed axially within the cylinder. Foils explode over
their entire surface within 10−7 s and can deposit a thin
metal layer onto an adjacent surface at up to 80 kbar
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
pressure.
Further details of wire explosion coating are available
elsewhere.6–13
WEAR AND EROSION RESISTANCE
Coating properties relevant to wear and erosion resistance
depend strongly on the nature of bonding to the substrate.1
Coatings of TiC, VC, WC, TiB , and TiN are mainly of
2 friction reduction; work hardening; surface amorphisation
metallic bonding character; nitrides, borides, and carbides
of aluminium, silicon, and boron are bonded covalently;
oxides of aluminium, titanium, beryllium, and zirconium
are bonded ionically. Important parameters are melting
point, stability, hardness, brittleness (toughness), adherence
to metallic substrates, and interaction tendencies. Further
selection criteria depend on environmental interactions,
fatigue properties, strength, and thermal expansion mis-
match with the substrate. Coating toughness tends to vary
inversely with hardness. A necessity for increased hardness
and strength implies decreasing toughness and adherence.14
Erosion resistance, inertness, low thermal conductivity,
and acceptable friction properties render the coatings
referred to above of value to the nuclear industry as well
as to traditional machine tool usage. Resistance to static
adhesion, in vacuum galling, wear scarring, friction without
lubricants, and chemical inertness have been reviewed
elsewhere.15 Hard metals provide suitable properties except
for their chemical response. Ionic hard materials provide
good surface finishes (high stability and low interaction),
but the best results are obtained using multiphase and
multilayer coatings.3,14,16–21 Data have been reported for
over 30 coatings.22,23 A CO–H microwave plasma has
2
been used to coat diamond onto WC–Co alloy tool
blades.24 No peel off occurred when using such blades with
an Al–Si workpiece at a speed of 450 m min−1 for 30 min.
Selective etching of the cobalt was found to promote
adhesion of the diamond to the tool surface.
The various possible forms of wear have been extensively
reviewed16,19,25 and include: adhesive wear (galling, scuffing,
and seizing) due to mutual solubility, especially in inert gas
and vacuum where no oxide layer exists; abrasive wear;
fretting wear as the result of low amplitude displacements;
delamination wear due to subsurface fatigue cracks;25
corrosive wear; and diffusion wear at high temperature,
due to weakness caused by selective element diffusion.
It is important to ascertain which of the above processes
is operating before an appropriate coating can be specified.
British Corrosion Journal 1999 Vol. 34 No. 3
Thin coatings will follow deformation of the substrate
when under load. If hot, interdiffusion, aging, and cyclic
effects can also occur.18 With mild abrasive wear, thin
coatings detach locally at grooves caused by abrasive
particles. Under erosion, thick coatings survive angular
particle impact well whereas thin coatings perform well
with blunt erodents. Internal stresses promote the spalling
of thin coats when eroded or scratched.26 High hardness
correlates fairly well with low adhesive and abrasive wear
for the same types of material and microstructure except
for wrought materials.27
High wear resistance is not necessarily linked to low
friction; soft materials might be effective lubricants but do
not wear well. A very hard smooth surface with small
inclusions of a soft metal or lamellar solid (e.g. MoS ) has
2
been recommended2 and is obtainable by ion implantation.
Coatings should be very thin for wear resistance, e.g. 2 mm
for MoS , owing to the necessity to conduct heat away
2
(this is difficult for MoS in a resin binder coating). Where
2
areas of wear are small (for example in bearings and small
regions on shafts) ion implantation is very suitable, being
inexpensive and resulting in no significant dimensional
change. For example, after 107 fretting cycles, 40%Ba was
still left in a barium ion implanted Ti–1Al–4V substrate.28
Nitrogen ion implantation can reduce mild abrasive wear
by a factor of 2–10 at temperatures below 400°C. Ion
implantation units can coat items up to 2 m in length,
800 mm in diameter, and 1000 kg in mass,29,30 e.g. car
crankshafts, printing cylinders, crushing rolls, plastic pro-
cessing moulds (see papers by Dearnley cited in Ref. 1).
The enhancement of wear resistance by ion implantation is
a consequence of: dislocation pinning by nitrogen, carbon,
or boron, or by obstacles such as finely dispersed nitrides;
for low friction; and surface oxidation by oxygen ions.1
Relatively recently discovered ‘quasicrystalline alloys’
have high hardness and can be used to plasma coat
aluminium alloys, copper, and steel.31 They have high
ductility and a friction coefficient lower than that of
aluminium alloys and about equal to that of low carbon
steel. However, they are suitable only for mild wear duty.
Carburising, nitriding, etc. are well known techniques for
enhancing wear resistance and are discussed in Ref. 1.
The requirements for optimum hot wear resistance
include:25 high hot hardness (no significant thermal soften-
ing); structural stability (temper resistance); retention of
adherent oxide films to act as lubricants; high thermal
fatigue resistance; and corrosion resistance.
Erosion occurs as a consequence of cutting wear of brittle
materials and deformation wear of ductile materials. Thus
the maximum erosion of brittle materials occurs by par-
ticle impacts perpendicular to the surface, but for ductile
materials it results from impacts at angles of 15–30°.19,32
No single coating can resist both high and low angle
impacts. The large variations in wear and erosion resistance
between different coatings have been reviewed elsewhere.1
Effect of oxides on high temperature wear
Sliding surfaces at 400–800°C for Ni–20Cr, Nimonic 75,
and electrodeposited cobalt composite with chromium
carbide particles (as a coating on Nimonic 108) have
displayed a variation of the friction coefficient with time.33
These surfaces all behaved similarly, following initial
differences, with friction coefficients of 0·5–0·7 and very low
wear rates. The low friction coefficients and wear rates
were associated with regions of shiny smooth oxide on the
load bearing surfaces. At 20°C, metal to metal contact
persisted (no significant surface oxidation occurred) and
so high friction and wear persisted, although the cobalt
composite had lower values of friction coefficient due to
the cobalt crystal structure.
 Sidky and Hocking Coatings for reducing wear and corrosion
DEPENDENCE OF HARD COATING
PROPERTIES ON COATING METHOD
PVD coatings
The high hardness of PVD coatings of TiC ranks second
only to diamond.34 Unfortunately, the PVD of wear
resistant TiC, TiN, and Ti(C,N) coatings onto low
temperature substrates usually results in poor adherence
and film morphology. Use of a low nitrogen pressure
improves adherence, as does a thin titanium film,35–37 and
vaporisation in C H +N .38 The hardness of boron
2 2 2 graphite.60 Siliciding of grey cast iron by CVD (using
phosphide coatings on molybdenum has been measured39
and was found to decrease as the B : P ratio was increased
from 1 to 1·5.
Very hard, wear resistant ceramic coatings may be
obtained by ARE, RS, and ion plating. Coatings of TiN
produced by reactive ion plating are used on twist drills,
cutting tools, dies, and moulds.35 Zirconium nitride is used
on cutting tools.40 Low temperature (below 400°C) depos-
ition of tribological 20%yttria–zirconia, TiB , and
2 Sprayed coatings
B–18 wt-%Si coatings on steels, copper alloys, and alumin-
ium alloys have also shown good wear resistance. Excellent
thermal and wear resistance have been displayed by
zirconia coatings on copper and aluminium alloys.41
Cathodic magnetron sputtering of molybdenum alloyed
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
with carbon or nitrogen gave coatings on type 304L steel
that were superior to hard chromium in corrosive, cyclically
stressed, and abrasive wear conditions.42,43
Modified arc evaporated TiN coatings have been found
to be more erosion resistant than those produced by other
PVD and CVD methods. A wide range of hardness values
has been reported for TiN, from 340 to 3000 HV, which is
thought to be mainly due to the crystallographic orientation
and presence of a second phase such as Ti N.44 Magnetron
2 3 2
sputtered Cr–C and Cr–N coatings have shown much
greater wear resistance than chromium.45 Solid solution
hardening of (Hf,Ti)N occurred when deposited by a
high rate reactive sputtering process using a dual cathode
configuration.46 Amorphous alumina coatings on grey cast
iron produced by rf magnetron sputtering have high
hardness and a tensile strength of 300 N m−2 (Ref. 47).
Ion implantation of interstitial species such as nitrogen
and carbon has major effects on surface related mechanical
properties.48–52 The lattice distortion is analogous to the
effect of shot blasting the surface and causes increased
hardness. The relation between wear and oxidation in ion
implanted metals has been discussed by Dearnaley53 who
found that ion implanted species on oxide grain boundaries
or dislocations block fast diffusion paths. Ion implantation
has been successful where oxidation and stresses coexist.
Ion implantation by inert gases acting on a sputtered TiB
2
film on stainless steel can improve the erosion resistance
to He+ and D+, which is of importance in connection with
the first wall of fusion reactors.54
Some workers have reported superior performance for
PVD coatings compared with their CVD counterparts.
These claims must be treated with caution since many
process and coating–substrate aspects must be taken into
account.1 A review has been undertaken of all CVD and
PVD processes.55 Furthermore, the effect of different PVD
processes on tool wear models has been discussed.17,23,55,56
Studies via TEM have confirmed that the high residual
compression growth stresses in all PVD coatings are
associated with lattice distortion and fine grain size.
CVD coatings
Chemical vapour deposited coatings have found many
interesting applications. For example, CVD coatings of
titanium, chromium, and aluminium carbides and TiN are
used to increase wear resistance in many machining
operations. Coatings of TiC, VC, NbC, and Cr C are used
7 3
on tools and valves, and in die casting, metal cutting, and
181
Magnox reactor applications to reduce sliding drag.25 Tools
carbide coated by CVD have been found to produce a
continuous chip when cutting steel and segmented chips
when cutting pearlitic cast iron. Tools coated with
TiN–Al O –TiC remain cooler by 200 K than uncoated
2 3
tools.57 A CVD coating of TiC on ball bearings shows very
good wear resistance and has extremely high hardness.58
Co-deposition of SiC with CVD pyrolytic carbon confers
increased wear resistance, suitable for rocket nozzles,59 and
high hot hardness has been reported for CVD SiC on
H +SiCl at 960–990°C) also produced an adherent and
2 4
wear resistant coating.61 Below 960°C, the adherence was
poor and above 990°C the coating was thin on parts
distant from the gas entry. A 30 mm CVD film of tantalum
is used on underground graphite heat receptors to resist
hot rock temperatures of 1427–1727°C.62 Very high hard-
ness at 1500°C has been reported for CVD Si N .63
3 4
Plasma and D-gun coatings are mainly used for wear
resistance (both adhesive and abrasive).27,64,65 Their
mechanical properties are anisotropic owing to their splat
structure and directional solidification. The hardness of a
D-gun coating is generally higher than that of a plasma
coating of the same composition, owing to its higher
density and cohesion.66 Hardness is usually reduced for a
given material if the coating is applied in an inert
atmosphere in comparison with spraying in air. It also
varies with cooling rate if relative differences in hardness
occur between the various phases which form.64 Erosion67
and fretting wear tests have been reported on D-gun
coatings of Cr C –NiCr and Cr C –NiCr on steels and
23 6
superalloys.
The wear mechanisms of thermally sprayed hardfacings
such as Ni B and carbides have been discussed in the
3
literature.68 Flame sprayed 13%Cr steel coatings are used
for wear resistance.69 Coatings of NiAl powder or
Ni–graphite (75%–25%) are flame sprayed to give abrad-
able seals.70 The lower density of flame sprayed as opposed
to plasma sprayed coatings is more appropriate for this
purpose. Grey cast iron has long been used for piston rings
in diesel engines as its graphitic structure prevents seizing.71
However, at high power the wear becomes unacceptable
and so hard chromium coatings have been applied, but
these require effective lubrication. Flame sprayed molyb-
denum (successful in petrol engines) corrodes in diesel
engines.
Plasma sprayed Mo–Mo C coatings resist wear, molyb-
2
denum being the ductile matrix. An inert atmosphere is
necessary to stop oxidation of the Mo C and loss of
2
molybdenum ductility. Such Mo–Mo C composite coatings
2
are reported to have low friction.72 Although plasma
deposited materials are softer than the wrought materials,
they are much more wear resistant. Wrought alloys produce
much debris but relatively little debris occurs for plasma
deposited alloys as their structure limits the size of adhered
wear particles. The addition of a small amount of alumina
to aluminium bronze results in almost the same wear
resistance as that of pure alumina, but without the increased
hardness.64
Arc sprayed mixed metal coatings and pseudoalloys (e.g.
copper+stainless steel ) are wear, erosion, and abrasion
resistant and can be deposited at high rates to give thick
coats on large components with bond strengths of about
30 N mm−2.
Electrochemical coatings and electroless
wear resistant coatings
The electrochemical and electroless processes include the
deposition of composite (cermet) using a slurry, aqueous
British Corrosion Journal 1999 Vol. 34 No. 3
 182 Sidky and Hocking Coatings for reducing wear and corrosion
electroplating, and metalliding by fused salt electroplating.
These are long established methods and extensive sources
of information are available.73–76 Chromium plating is a
traditional wear resistant coating, varying from 20 to
500 mm in thickness. Deposition conditions are important.77
Cermet electrodeposits of chromium carbide in a cobalt
matrix have excellent wear resistance.78,79 Electroless Ni–P
deposits also offer good wear resistance.80 Excellent high
temperature wear resistance is obtained using electrodeposi-
ted Co+Cr O cermets.81
2 3
CORROSION RESISTANCE
Problems with adhesion, composition, thickness, and
uniformity, as well as defects (pores, cracks, and disbonding,
in the as produced and/or heat treated condition), can
result in the failure of coatings under corrosive conditions
in service.
High temperature corrosion
Fluidised bed combustors such as coal gasifiers use Fe–Cr
based materials as main structural materials and these also
form the basis for coatings. The main problems are hot
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
corrosion and erosion.1 The environments encountered in
such applications are predominantly reducing (unlike those
in gas turbines), with oxygen partial pressure varying
cyclically from 10−1 to 10−14 bar and temperatures from
650 to 900°C. As steam and limestone are used in these
processes, the environment may contain H , H O, CaO,
2 2
CaSO , C, CO, CO , S , Cl , SO , H S, and HCl. The
4 2 2 2 2 2 materials can prevent spalling during thermal cycling and
furnaces operate at about 160 bar at 350°C and the heat
exchangers at 450–650°C.
Carburisation can occur in coal gasifier and fluidised
bed combustion. Silica coatings give good resistance to
carburisation at 825°C but are totally ineffective at 1000°C
where the silica is reduced to SiC. Even at 825°C, titanium,
manganese, and aluminium in the alloy partially reduce
the silica and some carburisation occurs. Silicide coatings
also fail to protect steels under these conditions.
The presence of gases such as H , H S, and H O, as well
2 2 2 all metal–ceramic coating systems. In particular, the adverse
as carburising gases, in coal gasifier atmospheres can
destroy the protection given by metal oxides which resist
carburisation. ‘Metal dusting’ by internal and external
carbide precipitation can be arrested by H S but sulphid-
2 substrates and the development of ranges of coating alloys,
ation may occur instead.
High temperature oxidation mechanisms form a very
extensive topic, reviewed in Ref. 1. In service, stresses due
to thermal cycling cause spalling, so adequate scale
plasticity is important and may be achieved by coating
alloy additives. In conditions which cause spalling, or
unlimited scale growth, selective depletion of the main
oxide forming element (e.g. chromium or aluminium) occurs
at the alloy/scale interface. This causes progressively longer
times for selective oxidation to retard the scaling rate to a
negligible value, and eventually this condition cannot be
achieved and other elements oxidise leading to failure.
Four factors are important for selective scale growth,
retention, and regrowth: the selective oxide must be capable
of good lateral growth; diffusion must be slow; the alloy
must have sufficient metal activity to replenish the selective
oxide, which must reform when damage, which is inevitable,
occurs; and the oxide must have excellent thermal fatigue
resistance.
The degradation of aluminide and silicide coatings is
the subject of detailed discussion elsewhere,1 as are the
important effects of minor elements on the corrosion of
high temperature materials.82,83
Cobalt base alloys offer better performance than nickel
and iron based alloys in many applications, especially in
high temperature corrosion.84
British Corrosion Journal 1999 Vol. 34 No. 3
Aqueous corrosion
A few examples of the use of metallic and ceramic coatings
for aqueous corrosion prevention are given below.
The porosity of flame sprayed ceramic coatings can be
greatly reduced by impregnation, for either low temperature
or high temperature corrosion resistance. Epoxy based
sealants are available for use at up to 150°C, e.g. bronze
shaft sleeves undercoated with an epoxy sealed plasma
sprayed chromia top coating gave good service for handling
brine in chlorine plant at 175°C. Aluminium bronze
coatings on the aluminium alloy substrates of aircraft
landing gear bearings corrode when the hydraulic fluid is
contaminated with sea water; a plasma coating identical to
the substrate, and its subsequent sealing, solved this
corrosion problem. Laser sealing of plasma sprayed Inconel
on stainless steel gave high corrosion resistance for marine
use. Laser fusion has been applied to aluminided and
chromided superalloys, electroplated chromium coatings,
and silica coatings for the same purpose.
Corrosion fatigue and pitting of low pressure steam
turbine blades (AISI 403 and 630 steels) and of other
surfaces exposed to steam condensate can be prevented by
Ni–Au electroplates, fused polytetrafluoroethylene, Ni–Cr
diffused electroplate, and vapour deposited aluminium
coatings.
CONCLUSIONS
Coatings are vital in many areas of advanced technology.
However, this is a developing field and much further
research is required, for example as discussed below.
Co-deposition of CVD pyrolytic carbon with other
this requires more detailed investigation. Fibre incorporated
CVD composites have many potential applications. More
work is required to prevent the hottest areas of MgO
stabilised zirconia coatings from degrading most rapidly
owing to MgO precipitation.
Improved diffusion barriers are required. Interface effects
and studies on how bondcoat interlayers adhere well to
ceramics are necessary. Interfacial energy data are also
required. Studies of adhesion promoters are required for
effects of surface embrittlement and inclusions on adhesion
require further research.
Predictions of the effect of specific coatings on given
each optimised to combat a particular environment,
are required.
Coatings forming dense glasses, complex oxides, or
spinels are required, particularly self-healing coatings for
long life.
Finally, there is a particular need for phase diagrams,
and both thermodynamic and diffusion data relevant
to coatings.
REFERENCES
1. . . , . . , and . . : ‘Metallic
and ceramic coatings – production, high temperature properties
and applications’; 1989, Harlow, Longman/New York, Wiley.
2. . , . . , . . , and . :
‘Ion implantation’; 1973, Amsterdam, North Holland.
3. . . , . . , and . . : T hin Solid Films,
1987, 153, 19.
4. . . , . . , and . . : J. Vac. Sci.
T echnol., 1974, 11, (4), 759.
5. . . , . . , and . : J. Mater. Sci.,
1991, 26, 4567.
6. . . : Proc. 4th Int. Conf. on ‘Advances in surface
engineering’; 1996, London, Royal Society of Chemistry.
7. . .  and . : J. Appl. Phys., 1960, 31, 1298.
8. . , . , . , and . : Proc. 7th
Int. Metal Spraying Conf., London, September 1973, Metal
Spraying Society, paper 26.
 Sidky and Hocking Coatings for reducing wear and corrosion
9. . , . , and . : Proc. 6th Int. Metal
Spraying Conf., Paris, September 1970, Metal Spraying Society,
paper B3.
10. . , . , and . : J. Jpn Soc. Powder Powder
Metall., 1970, 16, 338.
11. . : Yokendo, Tokyo, 1960, p. 150.
12. . .  and . .  (eds.): Proc. Conf. on ‘Exploding
wires’ 1959/1962/1964/1968, New York, Plenum Press.
13. In Ref. 12 (1959 edn), pp. 118 and 283.
14. . : J. Vac. Sci. T echnol. A, 1986, 4, (6), 2661.
15. . . . : J. Vac. Sci. T echnol. A, 1987, 5, 2930.
16. . : Int. Mater. Rev., 1988, 33, (3), 151.
17. . . : J. Vac. Sci. T echnol. A, 1988, 6, (3), 2149.
18. . . , . , and . : Mater. Sci.
Eng., 1987, 88, 177.
19. . . : J. Vac. Sci. T echnol. A, 1986, 4, (6), 2624.
20. . .  et al.: J. Vac. Sci. T echnol. A, 1986, 4, (6), 2770.
21. . .  and . . . : J. Vac. Sci. T echnol. A,
1986, 4, (5), 2259.
22. . . , . , and . . : Surf. Coat. T echnol.,
1987, 33, 105.
23. . .  and . . : J. Vac. Sci. T echnol. A, 1985, 3,
(6), 2439.
24. . , . , . , and . : J. Mater. Sci.,
1991, 26, 2937.
25. . . : in ‘Coatings for high temperature applications’,
(ed. E. Lang), 395; 1983, New York, Applied Science.
Downloaded by [UNAM Ciudad Universitaria] at 11:26 14 August 2017
26. . .  and . . : Surf. Coat. T echnol., 1987,
33, 191.
27. . . : in ‘Films and coatings for technology’, (ed. B. E.
Jacobson and R. F. Bunshah); 1981, Stockholm, Centre for
Education and Information.
28. . . : ‘Ion plating technology in films and coatings
for technology’, (ed. B. E. Jacobson and R. F. Bunshah), Vol. 1;
1981, Stockholm, Centre for Education and Information.
29. . . : ‘Recent developments in the United Kingdom
in ion implantation equipment for engineering components’,
Report, AERE, Harwell, 1987.
30. . . , . , and . : Surf. Eng.,
1987, 3, (3), 203–209.
31. . . , . . , and .  : J. Mater. Sci.,
1991, 10, 537.
32. . : ‘Erosion wear in coal utilization’; 1988, New York,
Hemisphere.
33. . .  and . . : in ‘High temperature corrosion’,
(ed. R. A. Rapp), 406; 1981, Houston, TX, NACE.
34. . .  and . . : J. Vac. Sci. T echnol., 1972,
9, 1389.
35. . . : ‘Nitrogen in hard coatings’, Technical
Memorandum TM 78838, NASA, Baltimore, MD, 1978.
36. . .  and . . : ‘Ti and N hard coatings’,
Technical Publication TP 1377, NASA, Baltimore, MD, 1979.
37. .  and . . : T hin Solid Films, 1980, 72, 541.
38. . , . , and . : Proc. 7th Int.
Conf. on Vacuum Metallurgy, Tokyo, April 1982, American
Vacuum Society, 209.
39. .  et al.: J. Mater. Sci., 1979, 14, (2), 496.
40. . : Proc. 7th Int. Metal Spraying Conf., London,
September 1973, Metal Spraying Society, 190.
41. . . : Surf. Coat. T echnol., 1986, 29, 247.
42. . , . , and . : T hin Solid Films, 1987,
153, 281.
43. . , . , and . : Surf. Coat. T echnol.,
1987, 33, 83.
44. . .  and . . : Surf. Coat. T echnol., 1987, 33, 169.
45. . , . , and . : Met. T echnol., 1983,
10, 115.
46. . . , . , and . . : T hin Solid
Films, 1987, 153, 159.
47. . , . . , and . : T hin Solid Films, 1987,
153, 123.
183
48. . : in ‘Ion implantation into metals’, (ed. V Ashworth
et al.), 102; 1982, Oxford, Pergamon.
49. . .  et al.: in ‘Ion implantation into metals’, (ed. V.
Ashworth et al.), 111; 1982, Oxford, Pergamon.
50. . - et al.: in ‘Ion implantation into metals’ (ed. V.
Ashworth et al.), 117; 1982, Oxford, Pergamon.
51. . . : in ‘Ion implantation into metals’, (ed. V. Ashworth
et al.), 126; 1982, Oxford, Pergamon.
52. . .  and . . : in ‘Ion implantation into metals’,
(ed. V. Ashworth et al.), 135; 1982, Oxford, Pergamon.
53. . : in ‘Ion implantation into metals’, (ed. V.
Ashworth et al.), 180; 1982, Oxford, Pergamon.
54. . .  and . : in ‘Ion implantation
into metals’, (ed. V. Ashworth et al.), 352 and 361; 1982,
Oxford, Pergamon.
55. . .  and . . . : J. Vac. Sci. T echnol. A,
1986, 4, (5), 2259.
56. . . : J. Vac. Sci. T echnol. A, 1986, 4, (6), 2810 and 2870.
57. . . , . . , and . . : T hin Solid Films,
1987, 153, 19.
58. . . , . , and . . : Surf. Coat.
T echnol., 1986, 29, 157.
59. .  and . . : T hin Solid Films, 1987,
152, 253.
60. . . : J. Vac. Sci. T echnol., 1974, 11, (4), 680.
61. . , . , . , and . :
J. Mater. Sci., 1986, 21, 1363.
62. . .  (.): ‘Protective coatings on metals’, Vol. 5;
1973, New York, Consultants Bureau.
63. .  and . : Proc. 7th Int. Conf. on Vacuum
Metallurgy, Tokyo, April 1982, American Vacuum Society, 180.
64. . . : J. Vac. Sci. T echnol., 1974, 11, (4), 725.
65. . . , . , and . . . : Proc. 7th Int. Metal
Spraying Conf., London, September 1973, Metal Spraying
Society, 62.
66. . . : ‘The contribution of metallic and ceramic
coatings to gas turbine engines’, contributed by Gas Turbine
Division, ASME, to Gas Turbine Conf. and Products Show,
Washington, DC, 1968.
67. . .  and . . : Surf. Coat. T echnol., 1987, 32, 237.
68. . - et al.: Proc. 7th Int. Conf. on Vacuum Metallurgy,
Tokyo, April 1982, American Vacuum Society, 352.
69. . . : ‘Flame spray coating for wear’, Society of
Automotive Engineers, Midyear Meeting, Chicago, IL, May
1969.
70. . : Werkstattstech. Z. Ind. Fertigung, 1975, 65, 619.
71. . . : Proc. 7th Int. Metal Spraying Conf., London,
September 1973, Metal Spraying Society, 194.
72. . . : in ‘Coatings for high temperature applications’,
(ed. E. Lang), 121; 1983, New York, Applied Science.
73. . .  (ed.): ‘Modern electroplating’; 1963, New
York, Wiley.
74. ‘Yearly handbook’, Canning and Co., Birmingham, UK.
75. . .  (ed.): ‘Encyclopedia of electrochemistry’; 1964,
New York, Elsevier.
76. . . .  and . . . : in ‘Modern electrochemis-
try’, 22; 1970, New York, Plenum.
77. . .  and . . : J. Vac. Sci. T echnol. A, 1985,
3, 2334.
78. . .  and . . : Plat. Surf. Finish., August
1978, 38.
79. . . , . , and . . : T rans. Inst. Met.
Finish., 1979, 57, 113.
80. .  and . . : Galvanotechnik, 1985, 76, 1650.
81. . : J. Vac. Sci. T echnol. A, 1986, 4, 2633.
82. . . : Proc. Conf. on ‘Role of minor elements on
performance of high temperature alloys’; 1993, London, The
Institute of Materials.
83. . . : in ‘High temperature materials chemistry: the
Charles Benjamin Alcock symposium’, (ed. B. C. H. Steele),
149–159; 1995, London, The Institute of Materials.
84. .  and . . : Proc. Conf. ‘Cobalt 93’,
London, 1993, Cobalt Development Association.
British Corrosion Journal 1999 Vol. 34 No. 3