Chapter-2

Coating and Thin Film Processing Technologies

Surface Engineering by Changing Surface Chemistry

Outline:
Chemical conversion coatings
Anodizing
Surface thermochemical treatment
Pack cementation coatings
Ion implantation
Laser alloying
Chromate chemical conversion coatings:
A chemical or an electrochemical treatment of metals or metallic
coatings in solutions containing hexavalent chromium (Cr6+) and,
usually, other components;

2Al 2Al3+ + 6e-

Cr2O72- + 8H+ + 6e- 2Cr(OH)3 + H2O
Formation of an amorphous protective coating composed of the
substrate, complex chromium compounds, and other components of
the processing bath;
Applied primarily to enhance bare or painted corrosion resistance,
to improve the adhesion of paint or other organic finishes, and to
provide the metallic surface with a decorative finish;
Widely used to finish aluminum, zinc, steel, magnesium,
cadmium, copper, tin, nickel, silver, and other substrates.
Auger electron spectroscopy (AES) depth profile of polished aluminum alloy
2024-T3 solid solution matrix exposed to Alodine 1200S conversion coating
solution for 5min
A film containing a mixture of the corrosion-resistant species and the major
elements found in the substrate. The mixture promotes strong adhesion of the
conversion coating to the substrate
SEM images of AA6060
surface before
chromating (a) and after
immersion in
chromating solution for
10s (b, c), 30s (d) and
3min (e, f). The
chromate conversion
coating is characterised
by a porous morphology
and incomplete
coverage at grain
boundaries (d, e).
After: O. Lunder, J.C.
Walmsley, P. Mack, and
K. Nisancioglu, Corrosion
Science, 47, 2005, p1604
TEM cross-sections of AA6060 specimen after immersion in chromating
solution for 3min, showing (a) incomplete coating coverage on the aluminium
matrix, (b) presence of a very thin CCC on intermetallic particle and (c)
apparent absence of a CCC at grain boundary zone.
Polarization curves for etched and chromated AA6060 in 0.1M
NaCl solution
Phosphate chemical conversion coatings:
Treatment with a dilute solution of phosphoric acid and other chemicals
in which the surface of the metal is converted to an integral, mildly
protective layer of insoluble crystalline phosphate (Me3(PO4)2xH2O/Zn,
Fe, Mn, Pb);

SEM pictures of crystalline phosphate layers on steel, four different types of

galvanized steel, and aluminum
 Typical process sequences in different industries

Typical sequence of pretreatment process for car bodies. D, dipping; S,

spraying; DI, deionized water.
 Immersion phosphating tank for batch coating of small components

Typical plant layout for a continuous conveyorized spray line for phosphating
Applications:

A base for paint;

A base for oil or other rust-preventive material;
Lubricity and resistance to wear, galling, or scoring of parts
moving in contact, with or without oil;
A surface that facilitates cold forming;
Temporary or short-time resistance to mild corrosion;
A base for adhesives in plastic-metal laminations or rubber-to-
metal applications;
Medium to heavy zinc phosphate coatings, and occasionally,
heavy manganese phosphate coatings are used for corrosion
resistance.
 SEM image of the zinc phosphate coating on the AZ91D magnesium alloy
obtained from the phosphating bath with the optimum concentration
ZnO + H3PO4 + H2O Zn(H2PO4)22H2O
Zn(H2PO4)22H2O ZnPO4- + H2PO4- + 2H2O
ZnPO4- Zn2+ + PO43-
3Zn+2 + 2H2PO4- + 4H2O + 6e- Zn3(PO4)24H2O +3H2
After: L.Y. Niu, Z.H. Jiang, G.Y. Li, C.D. Gu, J.S. Lian, Surface and Coatings
Technology, 200, 2006, p3021.
The qualities of phosphate coating depending on the content of
anticorrosion agent and pH of the phosphating bath
 Wear rate for a manganese phosphate coating produced by an
HNO3 accelerated solution
After: M. Khaleghi, D.R. Gabe, M.O.W. Richardson, Wear, 55, 1979, p277.
Cerium-based conversion coatings:

Cerium oxide conversion coating on an Al alloy

7075-T6 substrate
 After: B.F. Rivera, B,Y. Johnson, M.J.
OKeefe, and W.G. Fahrenholtz,
Surface and Coatings Technology, 176,
2004, p349.

AES depth profiling for a cerium oxide

conversion coating after phosphate post-
sealing

Surface morphology of a cerium oxide

conversion coating after 336h in salt fog
testing
Anodizing:
Aluminium anodizing:
An electrochemical method of converting aluminum (Al) into
aluminum oxide (Al2O3) at the surface;
Accomplished by making the workpiece the anode while suspended in
a suitable electrolytic cell;
Purposes: increase corrosion resistance; improve decorative
appearance; increase abrasion resistance; increase paint adhesion;
improve adhesive bonding; improve lubricity; provide unique,
decorative colors; provide electrical insulation; detection of surface
flaws; increase emissivity; permit application of photographic and
lithographic emulsions;
Acids used: sulfuric (H2SO4) and chromic (CrO3) acids;
Types of H2SO4 anodizing: room-temperature H2SO4 process
(conventional anodizing); low-temperature H2SO4 process (hardcoat
anodizing).
Typical process sequence for anodizing operations
CrO3 anodizing process:
CrO3 is much less aggressive toward aluminum than H2SO4, it should be
used whenever part design is such that rinsing is difficult;
Coating: nominally 2m thick, relatively soft, and susceptible to damage
through abrasion or handling;
Good repeatability coat a precise dimension to size;
Produces the least reduction in fatigue strength of the three coatings;
Color of CrO3 anodize will change with different alloy compositions and
the heat treat conditions test of the homogeneity of structural
components;
CrO3 anodize can be used as a mask for subsequent hardcoat anodize
operations;
Suitable for most alloys except high-silicon die-cast alloys and high-
copper alloys.
Chromic anodic layers formed on Al 2024 alloy, (a) at 20oC with 0M of oxalic
acid, (b) at 20oC with 0.02M of oxalic acid, (c) at 40oC with 0M of oxalic acid and
(d) at 40oC with 0.02M of oxalic acid.
After: V. Moutarlier, M.P. Gigandet, J. Pagetti, B. Normand, Surface and Coatings
Technology, 182, 2004, p117.
Sulfuric anodizing process:
Coating: normally 8m thick, may still be damaged by moderate handling
or abrasion;
A fairly hard surface, can be used in situations that require light to
moderate wear resistance: lubricated sliding assemblies and items subject to
handling wear, such as front panels;
Most aesthetically pleasing type of anodize used where final
appearance is important; can be dyed almost any color and produces deep,
rich shades that make the item appear to be made of a material bearing a
color throughout, rather than an applied coating;
Good corrosion resistance;
All alloy except high-silicon die-cast alloys can be successfully coated
with H2SO4 anodize.
Anodic oxide coatings on an Al-Si
alloy

After: X. Li, X. Nie, L. Wang, and

D.O. Northwood, Surface and
Coatings Technology, 200, 2005,
1994.
Hardcoat anodizing:
Coating: normally 50m thick, extremely hard (60-70HRC);
High hardness/wear resistance: valve/piston assemblies, drive belt pulleys, tool
holders and fixtures;
Excellent corrosion resistance: aluminum components in salt air, marine
components, automobile wash equipment, components for aircraft and aerospace
industries, and food preparation machines;
Excellent electrical resistor: insulate heat sinks for direct mounting of electrical
or electronic equipment and used in welding fixtures;
Porous: bonding or impregnation of other materials to aluminum is needed;
Salvage coating to restore worn or improperly machined parts to usable
dimensions;
Almost all alloys can be coated, the 6000-series aluminum alloys produce the
best hardcoat properties.
Cross-section of the aluminum oxide layer formed on aluminum at
6.0 Adm-2 (2.25 M H2SO4, 0 oC, 50 min)
After: L.E. Fratila-Apachitei, J. Duszczyk, L. Katgerman, Surface
and Coatings Technology, 157, 2002, p80.
Sealing of anodized coatings:
Purposes: partially converts the as-anodized alumina of an anodic coating to
an aluminum monohydroxide known as Boehmite close pores and to
eliminate the path between the aluminum and the environment;
Process: immersing the coating in hot water at a minimum temperature of
95oC for not less than 15 min;
Sealing softens the coating somewhat, hardcoat anodize is usually not sealed
unless criteria other than hardness have the maximum importance in the
finished coating.

Process of pore sealing with hydroxide during dipping in boiling

pure water (ASM Handbook Online)
Results of three-year seacoast exposure testing of anodized aluminum alloys
Highly ordered nanoporous
anodic alumina films
(AAO) formed in a sulfuric
acid solution.
After: S.Z. Chu, K. Wada, S.
Inoue, M. Isogai, and A.
Yasumori, Advanced
Materials, 17, 2005, p2115
Vertical fracture sections of porous
anodic alumina films
Alumina nanotube arrays Alumina nanowires

Carbon nanotube arrays Nickel nanowires

Anodizing non-aluminum substrates:
Magnesium anodizing:
Galvanic anodize or Dow 9 process: use internal voltage generated as a result
of a galvanic couple (steel cathode and Mg component); coating is dark brown
to black useful for optical components and for heat sinks in electronic
applications; an excellent paint base; have no appreciable thickness and impart
little added corrosion resistance;
HAE process: use an external power source and an alkaline bath; produce a
light tan subcoating at lower voltages and a thicker and dark brown phase at
higher voltages (hard and good abrasion resistant, but adversely affect the
fatigue strength of a base metal)
Dow 17 process: use an external power source and acidic solution (a
combination of ammonium bifluoride, sodium dichromate, and phosphoric
acid); produce a two-phase, two-layer coating: a light green or greenish tan
undercoating formed at lower voltages and a much heavier, second-phase,
vitreous, and dark green, brittle and highly abrasion resistant coating formed at
higher voltages.
A processing diagram, together with details of solution compositions and
operating conditions for galvanic anodizing (Dow 9 process)
(ASM Handbook Online)
HAE anodizing treatment procedures
and conditions (ASM Handbook
Online)
Dow 17 process (ASM Handbook Online)
 Al content

4m

Corrosion resistance
Roughness

Voltage

1m

0.5m

Anodizing of Mg alloys in alkaline solutions

After: Y. Mizutani, S.J. Kim, R. Ichino, M. Okido, Surface and Coatings
Technology, 169-170, 2003, p143.
Titanium anodizing:
Wear (to overcome its tendency to gall, anodized in caustic electrolytes);
Decorative colored coatings: anodizing in slightly acidified solutions of
phosphoric or sulfuric acid; vivid colors from magenta to cobalt blue can be
obtained by controlling the terminal voltage (jewelry industry, medical
implants, and dental instruments).

Barrier type amorphous anodic film on

sputter-deposited Ti-11.5at.%Mo alloy
by anodization in a 0.1moldm-3
ammonium pentaborate electrolyte at
293K for dielectric applications
(capacitors)
After: H. Habazaki, M. Uozumi, H. Konno, S.
Nagata, and K. Shimizu, Surface and
Coatings Technology, 169-170, 2003, p151.
Zinc anodizing:
Source materials: wrought or die cast zinc parts or zinc coatings
obtained by electroplating, mechanical deposition, thermal spraying, or
galvanizing;
A wide range of electrolytes (phosphates, silicates, or aluminates to
which are added chromates, vanadates, molybdates, and/or tungstates)
using either alternating or direct current;
Coatings: green, gray, or brown, depending on the electrolyte used;
Sealed using a material such as sodium silicate or an organic lacquer or
enamel for optimum corrosion resistance.
 Zinc anodized in a silicate-
based electrolyte operated at
18oC

After: N. Diomidis, and J.P.

Celis, Surface and Coatings
Technology, 195, 2005,
p307