Corrosion and Surface Engineering

MSE 3205

Topic: Coatings

Md Mehidi Hasan
Lecturer
Dept. of MSE,KUET

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Concept of the coatings

Coating - A layer of material, formed naturally or deposited artificially on the surface of an object made
of another material, with the aim of obtaining required technical or decorative properties.

The substrate, in other words, the coated object, or, in stricter terms, its superficial layer, constitutes one
phase of the system and the coating constitutes the second phase. Between the coating and the
substrate there exists an interface in the form of a layer of certain volume, with intermediate properties,
usually facilitating adherence of the coating to the substrate. In some coatings this layer bears the name
of intermediate.

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Structure of the coating

The coating has a laminar structure. Because of the great variety of coatings, both from the point of view
of material and technology, which stems from different designated uses, it is difficult to develop one
universal model of coating structure

Fig. 01: Schematic representation of coating structure: a) single layer; b) multi-layer

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1. The single layer coating (single coating, monolaminar) is a coating deposited on an appropriately
prepared substrate in one process or technological operation, comprising one layer of material.
Single layer coatings are divided into:
• Single constituent coatings - consisting of one material (element, compound), e.g. chromium, titanium
nitride TiN
• Multi-component coatings - consisting of several material components, e.g. alloying additives, titanium
carbonitride Ti(C,N) or titanium aluminonitride Ti(Al,N)

2. The multi-layer coating is one which consists of two or more materials.

These may be layers of the same material, separated by a sublayer, or they may be of different materials in
which case a sublayer may but need not necessarily be applied. The aim of applying multi-layer coatings is
the intensification of the protective or decorative or other function.

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Types of coatings

1. Classification of coatings by material 3. Classification of coatings by manufacturing methods

• Metallic coatings • Galvanizing

• Non-metallic coatings • Immersion coatings

• Spray coatings
2. Classification of coatings by application • Cladded coatings
• Protective coatings • Crystallizing coatings
• Decorative coatings
• Protective-decorative coatings
• Technical coatings

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Classification of coatings by material

Metallic coatings
Such coatings are made from different metals, metal alloys and metal composites, and deposited on
substrates, most often themselves metallic, by different methods.
Most often used metals are:
• Coating metals: zinc, nickel, chromium, aluminum, tin, cadmium, copper, lead, silver, gold, iron,
cobalt, indium, ruthenium, rhodium, palladium, and platinum. Often, refractory metals are also used,
such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten
• Alloys and coating composites: steels (particularly alloyed, corrosion and heat resistant), brasses as
well as alloys of metals: Pb-Sn-Cu, SnNi, W-Co, W-Ni, Ni-Fe, Co-Mo, Zn-Al, Zn-Fe, Zn-Ni, Zn-Mn, Zn-
Ce, ZnSn, Al-Si, Ni-Cr, Co-Cr, Ni-Al, Pb-Zn, Ni-B-Si, Ni-Cr-B-Si, Ni-Cr-B-Si-C, Co-Mo-Cr-Si, Ni-Cr-Al-Y.
Metallic coatings are usually deposited on expensive, precision components, rather small in size, which
may also be exposed to mechanical hazards in service conditions.

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Non-metallic coatings

These coatings, numerous and varied, are made from organic materials (paint, rubber, plastic) and inorganic (enamels,
ceramics), of natural and synthetic origin
Most often used coating materials are
• Paints - coating materials for covers, comprising suspensions of pigments (organic and inorganic coloring substances) in
a binder, manufactured in the form of liquids and powders.
• Varnishes - liquid (or powder) products, which are colloidal solutions of filmogenic substances
• Resins - amorphous organic substances of different chemical composition with consistence ranging from semi-liquid to
vitreous, not soluble in water, soluble in organic solvents or totally insoluble and non-melting
• Cements - binders, obtained synthetically from various materials
• Waxes - a group of complex organic substances of natural origin (animal, plant and mineral) or synthetic
• Asphalts - also called bitumins
• Lubricants - a general name given to all greasy substances which have the properties of diminishing friction between
surfaces, as well as those which protect the surface
and many more
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Classification of coatings by application

Protective coatings
Protective coatings are those coatings whose task is exclusively protection of the object from the harmful effect
of the environment, mainly the atmosphere and chemicals, as well as from mechanical hazards. These coatings
may also feature properties other than anti-corrosion, e.g., higher hardness, resistance to tribological wear, or
attractive appearance
Types of protective coatings:
• Anodic coatings : are made of metal which in a given environment exhibits a potential lower than that of
the substrate. In other words, they are made of a less noble metal than the protected substrate. This means
that upon mechanical or other damage of the coating or in the case of the presence of porosity, in the
presence of an electrolyte (when an elecrochemical cell is created) it is the substrate metal and not the
coating that is subjected to corrosion. Anodic coatings protect the substrate electrochemically. Examples of
anodic coatings are zinc, aluminum and cadmium plating on iron and steel.

Industrial purpose reason is in industry there is a temperature gradiant and corrosion is very common so the anodic coating helps to protect and it is in the reaction and it first start to
decay then after we notice we can change the coatung and thus it protect the substrate.
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• Cathodic coatings: are made of a metal whose electrode potential in given environmental conditions
is more electropositive than the potential of the substrate metal, i.e. made of a nobler metal than that
of the substrate. Consequently, they protect the substrate metal only when they are totally tight
(without porosity cracks, flaking, spalling and scratches). In the opposite event, as soon as the substrate
metal is exposed a galvanic cell is formed in the presence of an electrolyte. Examples of cathodic
coatings are nickel, copper, silver, lead, tin, and gold plating on iron and steel. The coating metal forms
the cathode, while that of the substrate - the anode. For these coatings, the most aggressive is
industrial atmosphere, less aggressive urban and seacoast, and least aggressive - rural
• Paint coatings effectively protect the metallic substrate only when they are multi-layered. Typical are
4-layered coatings: primer, surfacer, enamel, varnish. The anti-corrosion function is fulfilled mainly by
the primers, pigmented by elements with rustproof action, e.g., lead minium, zinc yellow and zinc dust.

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 I - beginning of corrosion;
II - advanced corrosion;
1 - scratch or pore;
2 - product of corrosion;
3 - pit-type loss

Fig. 02: Schematic representation of progress of coating corrosion: a) anodic

coating; b) cathodic coating.

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Decorative coatings

Decorative coatings, once called ornamental, serve predominantly to give the metal or non-metal object
an aesthetic external appearance. This depends first of all on color, luster and resistance to tarnishing and
also, perhaps, surface finish of the coating (hammer finish, webbling, crystal, crocodile skin), as well as
shine properties.

Among metallic coatings, electroplated coatings have found broadest use. Each metal or alloy has its own
characteristic color. Luster is dependent on surface smoothness, or it is obtained by the addition of so-
called lustering substances to the electrolyte bath.
Protective-decorative coatings
Protective-decorative coatings, sometimes also called decorative-protective, serve both to protect the
object against corrosion and light mechanical damage, and to give the surface an aesthetic appearance.
Regarding electrolytic coatings, the protective-decorative role is fulfilled by nickel, chrome, and copper-
nickel-chrome coatings on condition that they are sufficiently thick.
Corrosion protection is assured by sandwiched layers of nickel or copper and nickel. Sometimes,
sandwiched copper layers are replaced by brass but with the same thickness these offer poorer corrosion
protection than copper. Nickel is used for the protection of steel, copper and zinc substrates, as well as
those made of copper alloys or zinc alloys.
Technical coatings

Technical coatings serve to give the object certain physical properties: mechanical, electrical and thermal
Coatings which enhance tribological properties : In the majority of cases better tribological properties
are exhibited by harder than by softer metal coatings. Among non-metallic coatings, very high hardness
and excellent tribological properties are exhibited by nitride, oxide, carbide and boride coatings, deposited
in vacuum by PVD and CVD techniques.
Coatings which enhance electrical properties: These coatings serve first and foremost to enhance
electrical conductivity of terminals and are used in electrical and electronics applications.
Technological coatings: These coatings serve to enhance different properties of semi-finished products
during the execution of the technological process of manufacture or to protect the product against
diffusion by undesired elements
Corrective coatings: Such coatings are used to re-create the initial dimensions or shape of a component
partially worn in the course of service.
Geometrical parameters of coatings

1. Thickness

Coating thickness is the basic parameter on which protective properties, decorative and technical
properties significantly depend.
Porosity, tightness, corrosion resistance and mechanical strength all depend on the appropriate coating
thickness. Besides, for different types of coatings, this thickness has a different effect on usable
properties. For example, protective properties of coatings increase with the rise of thickness, similarly to
wear resistance. But thickness has the opposite effect on flexibility, impact strength, and sometimes even
on adhesion
Ranges of thickness and hardness of some coatings
2. Three-dimensional structure of the surface

The three-dimensional structure of the coating surface is the result of the coating process, dependent
on the method or technique used, on defects formed during the deposition and on substrate
roughness. The smoother they are, the lower their roughness. A measure of smoothness or roughness
of coatings is given by various parameters describing the unevenness of the surface.

3. Surface unevenness

Surface unevenness of the coating is described by the same parameters as those used in the
description of surface layers. Coatings may serve to deteriorate (e.g., ceramic sprayed and metallic
immersion coatings) or to enhance surface unevenness (e.g., some electroplated coatings smooth the
surface; paint coatings hide recesses). For the majority of coatings, particularly of the decorative
category, it is important to obtain small surface unevenness (high smoothness).
4. Defects of the three-dimensional structure

Defects of the three-dimensional structure, which are simply coating defects, all have the same
character as those of the surface layer. The most frequent defects, common to both surface layers and
coatings, are blemishes, scratches, cracks and porosity. Among the most important defects, common
to all coatings, are non-uniform thickness (including object edges), delamination, exfoliation,
incomplete coverage, pits, blisters, raising of the coating, brittleness, chipping, and sagging. Moreover,
each type of coating exhibits certain own, characteristic defects. Among the most frequently
encountered are:
• for metallic, electroplated coatings: burns, streaks, striation, haziness, roughness (here understood
as major build-ups or surface contamination inclusions), spots, decoloration, excessive matting and
runs and many more for organic and inorganic coatings.
Physico-chemical parameters of coatings

There are a lot of physico-chemical parameters of coatings. But one of the most important parameter is
residual stress.
Residual stresses are formed in coatings as the result of differences in thermal expansion coefficients of
substrate and coating materials (stresses of the I kind), as well as significant defects in the structure of
the coating material (stresses of the II and III kind). Usually, compressive stresses are favorable, while
tensile stresses are unfavorable. In order to reduce residual stresses of the I kind, multi-layered coatings
are deposited, comprising a composition of layers with successively changing thermal expansion
coefficients, relative to the substrate material. Residual stresses may be reduced by the selection of
appropriate materials and process parameters. The sign (kind) of stresses depends on the coefficients of
thermal expansion of substrate and coating layers and on the character of structural defects. If the layer
contains more atoms in interstitial positions than there are vacancies in the lattice, tensile stresses are
formed, while the reverse situation leads to the formation of compressive stresses
Type I, where sI refers to
macro-scale stress which
varies within the material
over a length-scale much
larger than the grain size.
Type II and Type III are
meso- and micro-scale
residual stress. Type II are
where sII changes on the
scale of a grain

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The methods of applying metal coatings are:

Electrodeposition
All metals can be electrodeposited from an electrolyte, but for most practical purposes non-aqueous baths
(organic solvent or fused salt) may be disregarded, so precluding metals such as aluminium and titanium
from application as electrodeposits. Chromium plate may be the best known but is in reality only a thin
layer of chromium on a thicker underlayer of nickel and/or copper.

Chemical or electroless plating

An aqueous reduction process in which metal is deposited from solution, often under a catalytic action,
may be adapted to promote deposition on a metal surface. The rate of deposition is usually slow and
invariant, making the process generally inflexible. Nickel is the most important metal deposited by this
method, but other metals have been chemically plated, especially for the initial coating of plastics prior to
conventional electro finishing.
Hot dipping

As the name implies, the metal coating is applied liquid to the component or substrate and may be
applied continuously or by batch processing. The formation of an alloy layer is an integral part of the
process and so adhesion is usually very strong. The method is best applied to low melting point metals
such as tin, lead, zinc and aluminium, and when relatively thick coatings (> 0.01 mm) are required. The
disadvantage of the process is that control of thickness is poor and thin deposits cannot be satisfactorily
produced. Tin on mild steel strip (tinplate for cans and containers) and zinc on mild steel (galvanized
steel) are the best-known products. The process is unsuitable for substrates which may be deleteriously
affected by the "heat treatment" of the molten metal bath.
Metal spraying

The application of a metal coating by spraying is particularly valuable for structural steelwork because
the spray gun can be portable, and a large finished structure can be coated in situ

Cladding

The roller bonding of a strip coating onto a flat substrate depends for success upon the formation of a
good adhesive bond between the metals(dissimilar). Temperature and roller or hydraulic pressure are the
two main variables, but removal of oxide layers at the interface is the practical problem. Copper may be
clad onto steel quite easily, but cladding of aluminium or stainless steel to mild steel is generally only
successful after careful surface preparation and welding or sintering as an aid to bonding.
Electrophoresis

Electrophoretic deposition provides a means of coating a substrate with a powdered metal or oxide but
must be followed by a heat treatment process in which the coating is sintered and adhered to the
substrate. The powder is present as electrostatically charged particles rather than ions in a polar solvent
such as alcohol.

Vacuum deposition

This technique may be used cold and does not depend upon characteristic metallic properties for the
substrate, so it may be used to coat non-metals. Metal is evaporated in vacuum and deposited onto the
substrate within the vacuum chamber. Low boiling point metals appear to be most suitable and because
of the limitations of electrodeposition, aluminium has received much attention.
Electrode Potential

Van't Hoff Isochore equation

The Van't Hoff Isochore equation relates the change in free energy ΔG° for a reaction to the equilibrium
constant Kp at constant pressure,

where n is the number of moles reacting, R is the gas constant and T is the temperature in degrees
Kelvin.

The equilibrium constant is defined as the ratio of the thermodynamic activities a of the products to those
of the reactants.
For example,

where Mn+ is the ion, e the electron and M° the metal. For the reaction to proceed forward, K (= aM/a Mn+)
must be large and positive, which makes ΔG negative. (Reactions with negative ΔG values are
thermodynamically spontaneous.)

The electrical potential which is necessary to drive such a reaction forwards is related to the free energy by

where n is the number of electrons involved per g-atom, F the Faraday ( = 96,493 C/equiv.) and E the
potential in volts.
When a metal is immersed in a solution containing its own ions a potential difference is established
between the metal and the solution and is given by the Nernst equation:

(Assuming all the constant values and at 25° C)

Change of concentration is regarded as a prime factor in affecting the metal electrode potential.

The standard electrode potential of a metal is an indication of its basicity or nobility. A metal having a
high negative E° value must have a large positive ΔG value for the ion reduction reaction, thus indicating
non-spontaneity.

Metals of this type (e.g. K, Na, Al) form very stable ions which in aqueous solution cannot be
electrodeposited. In contrast, metals having a positive E° value and hence negative ΔG values for ion
reduction (e.g. Cu, Ag) electrodeposit quite readily.
Standard (reduction) electrode potentials (25°C)

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 The change in electrode potential depends
upon the electron change, where univalent
ions have a larger effect than ions of higher
valency.

It is important to discriminate between

concentration and activity when complexing
agents are present: a large metal
concentration may be present in solution
although the activity of free metal ions may
be low at a level influenced by the stability of
the complex ion.
Variation of electrode potential with ion concentration for various metals.

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The use of complexants is a much more powerful method than concentration control in selective
deposition of one ion or co-deposition of two ions in electrodeposition

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Faraday's Laws

The two laws governing quantitatively the electrode reactions during electrolysis are:
1. The weight W of an element liberated in electrolysis is proportional to the current / and the time /, the
proportionality constant being the electrochemical equivalent Z

W = Zit
The product it expresses the number of coulombs of current passed
2. For a given coulomb level the weight of an element discharged is proportional to its chemical equivalent.
The Faraday F liberates a g-equivalent of an element of atomic weight A

itA
W= 𝑛𝐹

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During the electrolysis process all the ions in solution carry current and the contribution from an individual
ion depends upon its concentration and mobility. At the cathode an excess of positive cations builds up
and those with most positive discharge potentials are reduced; similarly at the anode those ions with most
negative discharge potentials are oxidized. More than one discharge process may occur at each electrode
and a redox reaction may be one.

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The cathode current efficiency for metal deposition is

Conversely the anode current efficiency refers to the dissolution process at a consumable anode

The value of the cathode current efficiency is an important economic consideration in an electropla ting process

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