SURFACE TREATMENT AND FINISHING

Module – 1
(Fundamentals of Electro plating, galvanizing, Hot dip metal coating, thin coating, thin coating, chromium
plating, Nickel plating. Vacuum coating, FVD & CVD metal spraying - Methods, surface preparation,
mechanical Properties of sprayed metals, plasma coating.)
ELECTRO PLATING:
Theory of Electroplating:
a) If a solution of metallic salt is used as an electrolyte, it ionizes when a potential difference is applied to
this through two electrodes. On ionization the metal ions migrate to the cathode and get deposited there. If
the electrolyte is the salt of the anodic metal itself the salt is reformed by the anode metal, which gets
ionized and goes into the solution. In this way, there is a continuous supply of metal ions, which are
deposited over the cathode.
b) Consider copper plating where the electrolyte is copper sulphate solution. The article is connected to
cathode and a copper plate is connected to anode as shown in Fig-1

Fig-1
c) When D.C. supply is given between anode & cathode the copper sulphate dissociates as
CuSO4 Cu++ + SO4- -
The positive Cu++ ions are attracted to cathode and get deposited over cathode surface (i.e. article) and the
negative SO4" ions move towards the anode. Now as anode is made of copper only, it ionizes as
Cu  Cu++ + 2e-
These Cu ions from anode plate combine with attracted SO4 - - ion in the electrolyte as
Cu++ + SO4- -  CuSO4
Thus the depleted electrolyte of Cu++ ions (as lost to deposit on cathode) is replenished with Cu ++ ions from
anode & the process run continuously as long as the supply is ON. Therefore finally in effect the material of
anode gets deposited on cathode in electroplating.
Principles of Electroplating:
Electrochemical plating is based on Faraday’s two physical laws. Briefly for our purposes, the laws
state:
(1) the mass of a substance liberated in electrolysis is proportional to the quantity of electricity passed
through the cell; and
(2) the mass of the material liberated is proportional to its electrochemical equivalent
(ratio of atomic weight to valence). The effects can be summarized in the equation
V = C x I x t -------------1
Where,
V = volume of metal plated, mm3 (in3);
C = plating constant, which depends on electrochemical equivalent and density,mm3/amp-s
(in3/amp-min);
I = current, amps; and
 t = time during which current is applied, s (min).
The product I x t (current x time) is the electrical charge passed in the cell, and the value of C
indicates the amount of plating material deposited onto the cathodic work part per electrical charge.
For most plating metals, not all of the electrical energy in the process is used for deposition; some
energy may be consumed in other reactions, such as the liberation of hydrogen at the cathode. This reduces
the amount of metal plated. The actual amount of metal deposited on the cathode (work part) divided by the
theoretical amount given by Eq. (1) is called the cathode efficiency. Taking the cathode efficiency into
account, a more realistic equation for determining the volume of metal plated is
V = ECIt -----------------2
Where,
E = cathode efficiency, constant C
The average plating thickness can be determined from the following:
d = V/A
where,
d = plating depth or thickness, mm (in);
V = volume of plate metal from Eq. (2); and
A = surface area of plated part, mm2 (in2).
Electro Plating Process:
Plating involves the coating of a thin metallic layer onto the surface of a substrate material. The
substrate is usually metallic, although methods are available to plate plastic and ceramic parts. The most
familiar and widely used plating technology is electroplating. Electroplating, also known as electrochemical
plating, is an electrolytic process in which metal ions in an electrolyte solution are deposited onto a cathode
work part.
The anode is generally made of the metal being plated and thus serves as the source of the plate
metal. Direct current from an external power supply is passed between the anode and the cathode. The
electrolyte is an aqueous solution of acids, bases, or salts; it conducts electric current by the movement of
plate metal ions in solution. For optimum results, parts must be chemically cleaned just prior to
electroplating. The arrangement is shown in Fig-2

Fig-2
Electro plating parameters:
A. Bath Parameters:
1. Solution composition and concentration
2. Type of metallic salts (effect of anion type)
3. Type and concentration of complexing agents
4. Solution pH and pH buffer
5. Additives (brightener, leveling agent, stress reducer, supporting electrolyte)
B. Operating Parameters:
1. Substrate material (metal, non-metal)
 2. Pre-treatment of substrate materials (deoxidation, degreasing, washing, drying)
3. Current density: (Direct current (DC); Pulsed direct current (PDC); Pulsed reverse current (PRC);
Potentiostatic (P); Pulsed potentiostatic (PP)
4. Overpotential
5. Agitation (static, stirrer, bubbling, ultrasonic, vibration etc.)
6. Plating temperature
7. Other: Shape of electrolyzer, type of anode materials (soluble, non-soluble)
The typical working parameters are listed in table 1 & 2

Various methods and applications being followed for electroplating process:

A variety of equipment are available for electroplating, the choice depending on part size and
geometry, throughput requirements, and plating metal.
The principal methods are
(1) Barrel plating, (2) Rack plating, and (3) Strip plating.
Barrel plating : It is performed in rotating barrels that are oriented either horizontally or at an oblique angle
(35º). The method is suited to the plating of many small parts in a batch.
Electrical contact is maintained through the tumbling action of the parts themselves and by means of
an externally connected conductor that projects into the barrel. There are limitations to barrel plating; the
tumbling action inherent in the process may damage soft metal parts, threaded components, parts requiring
good finishes, and heavy parts with sharp edges.
Rack plating is used for parts that are too large, heavy, or complex for barrel plating. The racks are made of
heavy-gauge copper wire, formed into suitable shapes for holding the parts and conducting current to them.
The racks are fabricated so that work parts can be hung on hooks, or held by clips, or loaded into baskets. To
avoid plating of the copper itself, the racks are covered with insulation except in locations where part contact
occurs. The racks containing the parts are moved through a sequence of tanks that perform the electroplating
operation.
Strip plating is a high-production method in which the work consists of a continuous strip that is pulled
through the plating solution by means of a take-up reel. Plated wire is an example of a suitable application.
Small sheet-metal parts held in a long strip can also be plated by this method. The process can be set up so
that only specific regions of the parts are plated, for example, contact points plated with gold on electrical
connectors.
Characteristics of the most commonly used coating materials:
Common coating metals in electroplating include zinc, nickel, tin, copper, and chromium. Steel is the
most common substrate metal. Precious metals (gold, silver, platinum) are plated on jewelry. Gold is also
used for electrical contacts.
Zinc: Zinc-plated steel products include fasteners, wire goods, electric switch boxes, and various sheet-
metal parts. The zinc coating serves as a sacrificial barrier to the corrosion of the steel beneath. An
alternative process for coating zinc onto steel is galvanizing.
Nickel: Nickel plating is used for corrosion resistance and decorative purposes over steel, brass, zinc die
castings, and other metals. Applications include automotive trim and other consumer goods. Nickel is also
used as a base coat under a much thinner chrome plate.
Tin: Tin plate is still widely used for corrosion protection in ‘‘tin cans’’ and other food containers. Tin plate
is also used to improve solderability of electrical components.
Copper: Copper has several important applications as a plating metal. It is widely used as a decorative
coating on steel and zinc, either alone or alloyed with zinc as brass plate. It also has important plating
applications in printed circuit [Link], copper is often plated on steel as a base beneath nickel and/or
chrome plate.
Chromium: Chromium plate (popularly known as chrome plate) is valued for its decorative appearance and
is widely used in automotive products, office furniture, and kitchen appliances. It also produces one of the
hardest of all electroplated coatings, and so it is widely used for parts requiring wear resistance (e.g.,
hydraulic pistons and cylinders, piston rings, aircraft engine components, and thread guides in textile
machinery).
GALVANIZING:
Process of Galvanizing or Describe surface treatment through Galvanizing:
Galvanizing is the process of applying zinc coating to a more noble metal (popularly steel or iron) to
prevent corrosion (rusting). Hot-dip galvanization is the most well-known method in which the steel part is
submerged in a bath of molten zinc. In the bath, the iron in the steel metallurgically reacts with the molten
zinc to yield a tightly bonded uniform alloy coating, which provides superior corrosion protection to steel.
The simplicity of the process provides it with a distinct advantage over other corrosion protection methods.
Moreover, galvanizing produces higher thickness coating (about 80 µm) of zinc compared to electroplating
(about 25 µm).
Main steps within the galvanizing process include :
1. Cleaning cycle – decreasing and chemical clean
2. Fluxing – helps to wet the surface of the steel
3. Galvanizing – immersion of steel into bath of molten zinc
4. Post treatment (optional)
1. Cleaning: Cleaning process should be chosen for the substrate to coat depends upon the contaminant such
as degreasing, pickling etc..
2. Fluxing: The steel is dipped in the flux. The purpose of the flux is to clean the steel of all oxidation
developed since the pickling of the steel and to create a protective coating to prevent any oxidation before
entering the galvanizing kettle. The flux is, therefore, a chemically active reductant, which by being placed
on the surface of the liquid metal bath prevents excessive dross formation.
Chlorides form most satisfactory fluxes because on hydrolysis they release hydrochloric acid:
ZnCl2 + H2 0 = Zn(OH)Cl + HCl,
or ZnCl2 + 2H20 = Zn(OH)2 + 2HCl.
The acid so released then removes what oxide is present:
FeO + 2HC1 = FeCl2 + 2H20.
In addition to zinc chloride, sodium and ammonium chlorides may also be present and if used in the
fused state a drip feed of water is important
3. Galvanizing: Once the steel has been completely cleaned, and after fluxing it is ready for immersion in
the zinc bath. The galvanizing kettle contains zinc specified to ASTM B6, a document that specifies any one
of three grades of zinc that are each at least 98% pure. Sometimes other metals may be added to the kettle to
promote certain desirable properties in the galvanized [Link] galvanizing kettle (Figure 3), is heated to
a temperature ranging from 820-860 F (438-460 C), at which point the zinc is in a liquid state. The steel
products are lowered into the galvanizing kettle at an angle, and stay in the bath until the steel heats to the
bath temperature. Once the diffusion reaction of iron and zinc is complete, the steel product is withdrawn
from the zinc kettle. The entire dip usually lasts less than ten minutes, depending upon the thickness of the
steel.
Corrosion Resistance. Zinc coatings protect steel in three ways:
 Initially, a continuous film of zinc at the surface of steel serves as a barrier to separate the steel from
theenvironment.
 At voids in the coating, such as scratches and cut edges, the zinc behaves as a sacrificial anode to
provide galvanic protection.
  After anodic dissolution of the zinc metal, zinc hydroxide can precipitate at the cathodic areas of
exposed steel, thus forming a secondary barrier.
The corrosion loss of a hot dip zinc coating is generally considered to be linear. Because of this, the life
of a zinc coating is proportional to its thickness. In the industrial environment of Bethlehem, PA (see Fig. 4),
the corrosion loss is approximately linear with time at an average rate of about 2 μm/year (Ref 18). Near-
linear behavior is also observed in marine and rural environments.

Fig-3 Fig-4
Applications:
Galvanized coatings are applied to iron and steel primarily to provide protection against corrosion of
the base metal.
Some major applications of hot dip galvanized coatings include:
 Structural steel for power generating plants, petrochemical facilities, heat exchangers, cooling coils,
and electrical transmission towers and poles
 Bridge structural members, culverts, corrugated steel pipe, and arches
 Reinforcing steel for cooling towers, architectural precast concrete, and bridge decks exposed to
chlorides
 Pole line hardware and railroad electrification structures
 Highway guard rails, high-rise lighting standards, and sign bridge structures
 Marine pilings and rails
 Grates, ladders, and safety cages
 Architectural applications of structural steel, lintels, beams, columns, and related building materials
 Galvanized and painted structural steel for aesthetic, color-coded or extended-life applications,
including communication towers, pipe and sign bridges, railings, fencing, and agricultural
equipment. Wastewater treatment facilities, composting buildings, catwalks, gratings, railings,
support steel, and related non immersion applications.
HOT DIP METAL COATING:
Process of hot dip metal coating:
Definition: Hot dipping is a process in which a metal substrate is immersed in a molten bath of a second
metal; upon removal, the second metal is coated onto the first. Of course, the first metal must possess a
higher melting temperature than the second.
The most common substrate metals are steel and iron. Zinc, aluminum, tin, and lead are the common
coating metals. Hot dipping works by forming transition layers of varying alloy compositions. Next to the
substrate are normally inter metallic compounds of the two metals; at the exterior are solid solution alloys
consisting predominantly of the coating metal. The transition layers provide excellent adhesion of the
coating. The primary purpose of hot dipping is corrosion protection.
Two mechanisms normally operate to provide this protection:
(1) Barrier protection: the coating simply serves as a shield for the metal beneath; and
(2) Sacrificial protection: the coating corrodes by a slow electrochemical process to preserve the
substrate.
Different types of hot dip metal coating:
Hot dipping goes by different names, depending on coating metal:
[Link] is when zinc (Zn) is coated onto steel or iron;
[Link] refers to coating of aluminum (Al) onto a substrate;
[Link] is coating of tin (Sn); and terneplate describes the plating of lead–tin alloy onto steel.
Galvanizing: is applied to finished steel and iron parts in a batch process; and to sheet, strip, piping, tubing,
and wire in an automated continuous process. Coating thickness is typically 0.04 to 0.09 mm (0.0016–
0.0035 in). Thickness is controlled largely by immersion time. Bath temperature is maintained at around
450ºC (850ºF).
Aluminizing: Commercial use of aluminizing is on the rise, gradually increasing in market share relative to
galvanizing. Hot-dipped aluminum coatings provide excellent corrosion protection, in some cases five times
more effective than galvanizing .
Tin plating: Tin plating by hot dipping provides a nontoxic corrosion protection for steel in applications for
food containers, dairy equipment, and soldering applications. Hot dipping has gradually been overtaken by
electroplating as the preferred commercial method for plating of tin onto steel.
Terneplating: involves hot dipping of a lead–tin alloy onto steel. The alloy is predominantly lead (only
2%–15% Sn); however, tin is required to obtain satisfactory adhesion of the coating. Terneplate is the lowest
cost of the coating methods for steel, but its corrosion protection is limited.
Continuous Hot Dip Sheet-Coating Processes:
In continuous hot dip coating of steel sheet, coils of steel are welded end-to-end and are coated at
speeds of up to about 200 m/min (650 ft/min).
Hot Lines: In hot processing, steel strip is cleaned and heated in a reducing gas atmosphere, typically a
mixture of hydrogen and nitrogen, in order to prepare the surface for coating. Annealing of cold-rolled steel
by heating above its recrystallization temperature of about 700 °C (1300 °F) is usually a part of this heating
process. Combining the steps of cleaning, heat treating, and bringing the sheet to coating temperature into a
continuous operation contributes to making the hot process economical. Hot processing at lower
temperatures without recrystallization is also done to produce fullhard, coated, high-strength sheet. Lower
temperatures are also used to coat hot-rolled sheet, or to coat cold-rolled sheet that has been previously
annealed.
Surface preparation: Following cleaning, the sheet passes into a radiant tube furnace containing a mixture
of hydrogen and nitrogen that reduces surface iron oxides. This atmosphere produces a very clean surface
that can be easily wet by the coating metal. Heating of the steel also takes place in the furnace. Annealing of
cold-rolled sheet is achieved by heating usually just above the temperature for subcritical recrystallization
(about 720 °C, or 1330 °F). Following recrystallization, it is generally desirable to cool the sheet down to
near the bath temperature (about 460 °C, or 860 °F in the case of zinc coatings) in order to avoid overheating
of the metal bath. Most modern lines have jet coolers to convectively cool the strip before bath entry.
Process: The steel strip next enters a pot containing a bath of the molten coating metal. Shown
schematically in Fig. 5, the pot region is where the actual hot dip coating process takes place. The first
coating pots were little more than steel tubs heated by gas flames. Modern pots are steel vessels lined with
ceramic refractory and heated by electric induction. Any hardware in the bath, such as the rolls, bearings,
and support members, is usually made of 316 stainless steel or a similar alloy in order to resist attack by the
molten metal.
 Fig-5
As the strip exits the pot, a film of molten coating adheres to the surface. The thickness of the molten
film is controlled by passing the strip between gas wiping dies, which remove excess coating metal with a
stream of gas. Coating thickness is determined by the geometry of the wipers, the velocity of the wiping gas,
and the distance between the wiping dies and the sheet. The wiping gas may be steam, air, or nitrogen. On-
line x-ray fluorescence or isotope gages continuously monitor the actual coating thickness and enable rapid
adjustments to be made.
CHROMIUM PLATING:
Chromium has several obvious advantages in stability of price, availability, attractive appearance,
but also in the fact that its tenuous oxide film (Cr203) also offers additional tarnish resistance and excellent
bond possibilities for lacquer top coatings. Chromium is bluish-white and lustrous metal that is resistant to
corrosion in most atmospheres. Chromium plating, therefore, is extensively used as a final finishing
operation.
Principles:
Chromium cannot be deposited from a solution containing only chromic acid (CrO3) and water.
There must also be at least one or more acid radicals present to act as catalyst and aid in the cathodic
deposition of chromium. Those most commonly used are sulfate and fluoride, the latter generally in the form
of a complex fluoride. For successful operation, the ratio of chromic acid to total catalyst acid radicals must
be maintained within definite limits, preferably about 100:1 in the case of sulfate and other ratios for
fluoride and related catalyst ions. The voltages required are higher than in most other electroplating
processes: generally 4 - 10 V, depending on operating conditions. Consequently, the electrical energy
required for chromium plating is higher than that for most other metal plating,
Types of chromium plating:
There are two principal classes of chromium plating: "decorative, in which thin coatings serve as a
non-tarnishing, durable surface finish; and industrial or "hard" chromium, where heavy coatings are used to
take advantage of the special properties of chromium, which include resistance to heat, wear, corrosion,
erosion, low coefficient of friction and anti galling.
Process: The electrolysis of pure chromic acid solutions produces only hydrogen evolution under most
conditions. In fact, hydrogen evolution at the cathode and oxygen evolution at the anode are two reactions
that can be achieved when any conductive liquid has an electric current passed through it. The diagram (Fig-
6) below shows these reactions for an aqueous solution of sodium chloride (NaCl).
 Fig-6
The first two reactions show the disassociation of NaCl and H2O. These reactions occur in any
aqueous solution. The double arrow indicates the reaction can go in either direction. Reactions #3 and #4,
however, can only occur under the influence of an electric current where electrons flow from the cathode to
the anode. The third reaction shows how two positive hydrogen ions and two electrons produce the neutral
hydrogen molecule that leaves the solution as a gas. The fourth reaction shows how four negatively charged
hydroxide ions loose their four electrons to produce two water molecules and the neutral oxygen molecule,
which also leaves the solution as a gas.
The chemical reactions in a chrome plating system are not quite that simple. Besides oxygen and
hydrogen evolution, a positively charged chromium complex is reduced to chromium metal on the cathode
surface; some Cr (VI) is also partially reduced to Cr (III) at the cathode surface. Hoare's proposed
mechanism describes how the sulfate and other catalytic ions play a dual role in the reduction of Cr (VI) to
Cr metal. First, it acts as a blocking agent so that the desired chromic-dichromate complex can be formed.
Second, it catalyzes the reduction of Cr (II) to Cr metal, which cannot be obtained without the formation of
chrome-sulfate complexes.
The reactions as follows,

Applications of Decorative chromium plating:

 Decorative chromium plating application is very popular in the automotive industry, in which
durability, corrosion resistance, and aesthetics are all greatly valued. It is not uncommon to see a
decorative chromium plating on elements of both cars and motorcycles; such as rims, engine
components, exhausts, and more.
 It is also a great fit for kitchen utensil design requirements.
  Other common applications can be seen in premium tools and taps.
Applications of hard/engineering chromium plating:
 It’s also used in the automotive industry, but for critical engineering applications: shock absorbers,
cylinders, and other components that are prone to work under high cycles over extended periods of
time. Such components receive hard chrome plating in order to meet durability and lubricity
requirements.
 It has a wide variety of applications in the aerospace industry as well. Some hard chrome plated
components in this industry are: landing gear and aluminium piston heads, in order to provide an
optimal performance while keeping weight minimal; actuator elements, so as to prevent wear and
extend their service life.
 Gears are usually hard chrome plated because of the galling-prevention and lubricity benefits this
coating provides. This is translated into enhanced performance and the extension of service life in
low-friction applications.
 It’s also often used in worn parts as filling material in order to restore original dimensions.
Typical process parameters:

NICKEL PLATING:
Faraday's Law for Nickel. The amount of nickel deposited at the cathode and the amount dissolved
at the anode are directly proportional to the product of the current and time (Faraday's Law). The
proportionality constant is equal to M divided by nF, where M is the molecular weight, n is the number of
electrons involved in the electrochemical reaction, and F is Faraday's constant, equal to 96,500 coulombs
(ampere-seconds). For nickel, the constant is 1.095 g/A · h. The constant for nickel deposition is calculated
assuming that cathode efficiency is 100%; because a small part of the current goes to discharge hydrogen,
the constant must be adjusted by multiplying by the cathode efficiency (for example, 1.095 × 0.955 =
1.046).
Process:

Fig-7
 Nickel plating is similar to other electroplating processes that employ soluble metal anodes. It
requires the passage of direct current between two electrodes that are immersed in a conductive, aqueous
solution of nickel salts. The flow of direct current causes one of the electrodes (the anode) to dissolve and
the other electrode (the cathode) to become covered with nickel. The nickel in solution is present in the form
of divalent positively charged ions (Ni++). When current flows, the positive ions react with two electrons
(2e-) and are converted to metallic nickel (Ni0) at the cathode surface. The reverse occurs at the anode,
where metallic nickel is dissolved to form divalent positively charged ions, which enter the solution. The
nickel ions discharged at the cathode are replenished by those formed at the anode. The arrangement of
deposition process is shown in figure 7.
Hydrogen Evolution and Cathode Efficiency.
The discharge of nickel ions is not the only reaction that can occur at the cathode; a small percentage
of the current is consumed in the discharge of hydrogen ions from water. This reduces the cathode efficiency
for nickel deposition from 100% to 92 to 97%, depending on the nature of the electrolyte. The discharged
hydrogen atoms form bubbles of hydrogen gas at the cathode surface.
Anode Efficiency.
Under normal conditions the efficiency of dissolution at the anode is 100% and no hydroxyl ions are
discharged from the water. If the pH of the solution is too high, however, hydroxyl ions may be discharged
in preference to the dissolution of nickel, and oxygen will be evolved. Under those conditions, the nickel
anode becomes passive and ceases to dissolve nickel. Activated nickel anode materials are available
commercially that resist the onset of passivity and replenish the solution with nickel ions over a wide range
of plating conditions.
The Watts Solution and Deposit Properties
The watt solution remains the basis of most decorative nickel plating processes, and it is used for
engineering applications and for electroforming. It is operated at elevated temperatures and is capable of
being used with high current densities.
The constituents of the Watts bath have several functions.
 Nickel sulfate is available in commercially pure forms, is relatively inexpensive, and is the major
sourceof the nickel ions in solution. A high nickel sulfate concentration is used when high current
densities are required.
 Nickel chloride serves primarily to improve anode corrosion, but it also increases conductivity and
uniformity of coating thickness distribution. Excessive amounts of chloride increase the corrosivity
of the solution and the internal stress of the deposits and may cause plating problems if excessively
high.)
 Boric acid is used in nickel plating solutions for buffering purposes; its concentration may affect the
appearance of the deposits. The deposit may first become frosty in high current density areas at 30
g/L (4 oz/gal) of boric acid, and then as the boric acid concentration approaches 15 to 23 g/L (2 to 3
oz/gal), the deposit may be burnt and cracked. No effect on appearance is observed at high boric acid
concentrations up to saturation (45 g/L, or 6 oz/gal).
 Wetting agents or surfactants, formulated specifically for nickel plating solutions, are almost always
added to control pitting. Their function is to lower the surface tension of the plating.
VACUUM COATING:
Principle of vacuum coating:
The types of coatings include metals (e.g., cadmium, chromium, copper, nickel, titanium) and
nonmetals (e.g., ceramic matrix composites of carbon/carbon, carbon/silicon carbide, etc.), deposited in thin
layers (i.e. atom by atom or molecule by molecule) on the surface (Fig. 8).
Vapor deposition technologies include processes that put materials into a vapor state via
condensation, chemical reaction, or conversion. When the vapor phase is produced by condensation from a
liquid or solid source, the process is called physical vapor deposition (PVD). When produced from a
chemical reaction, the process is known as chemical vapor deposition (CVD).
 Fig-8
The vapor deposition processes form a thin coating on a substrate by either condensation or chemical
reaction of a gas onto the surface of the substrate. The two categories of processes that fall under this
heading are physical vapor deposition and chemical vapor deposition. In these processes, the layer of
deposited material is very thin – only a few microns. In the vacuum evaporation process, the metal to be
deposited is heated in an enclosed oven at high temperature and very low pressure; some of the metal vapor
deposits as a thin layer on the part. The surface can be coated not only with metal, but also with some
carbides, nitrides, or ceramics. Typical applications include surface coating of cutting tools, e.g. drills,
reamers, punches, dies etc.
Principle of Vacuum deposition:
The principle is generally to react the metal with a vapour reactant at one temperature and
decompose it at another temperature, the reaction being expressed in a general equation of type
M +n(XY) = M(XY)n
and the free energy of reaction given by:
∆G° = -a + bT.
For such a reaction the standard free energy is negative at low temperatures and positive at high
temperatures, so that at T < alb reaction is forward and for T > a/b reaction is backward. However, because
the reaction represents a reduction in molecules of the gaseous phase, if n > 1 the reaction is pressure-
sensitive and this represents an important reaction variable. Other limitations may include dissociation of the
metal compound to form alternative products, e.g.
M(XY)„ = MX„ + nY.
The reactant gas may also dissociate, e.g.
2XY = X + XY2,
or the metal compound may dissociate in stages,
M(X Y)n = M ( X Y)n-1 + X Y
Μ(ΧΥ)n-1 = M(XY)n_2 + XY . . . etc.
The most convenient reaction of this type involves the use of carbon monoxide to form metal
carbonyls, but while a range of transition metals form carbonyls only nickel carbonyl has been examined in
any detail for coating deposition/51} In this case the tetracarbonyl forms at about 45°C and dissociates at
about 200°C (1 atm pressure), above which temperature carbon co-deposition may occur by
2CO - C + C02
Nickel does not form a carbide, but both molybdenum and tungsten do; this can be avoided by
adding moist hydrogen to the vapour system. Iodine forms iodide vapour in a similar manner although the
temperatures involved are very much greater, dissociation at 1500°C and 0-01 atm pressure being necessary.
PHYSICAL VAPOUR DEPOSITION:
Principle:
Physical vapor deposition (PVD) is a group of thin film processes in which a material is converted
into its vapor phase in a vacuum chamber and condensed onto a substrate surface as a very thin layer. PVD
can be used to apply a wide variety of coating materials: metals, alloys, ceramics and other inorganic
compounds, and even certain polymers. Possible substrates include metals, glass, and [Link],
PVDrepresents a versatile coating technology, applicable to an almost unlimited combination of coating
substances and substrate materials.
 All physical vapor deposition processes consist of the following steps: (1) synthesis of the coating
vapor, (2) vapor transport to the substrate, and (3) condensation of vapors onto the substrate surface. These
steps are generally carried out inside a vacuum chamber, so evacuation of the chamber must precede the
actual PVD process.
The properties of a film of a material formed by any PVD process depends on four factors:
 Substrate surface condition--e.g., surface morphology (roughness, inclusions, particulate
contamination), surface chemistry (surface composition, contaminants), mechanical properties,
surface flaws, outgassing, preferential nucleation sites, and the stability of the surface
 Details of the deposition process and system geometry--e.g., angle-of-incidence distribution of the
depositing adatom flux, substrate temperature, deposition rate, gaseous contamination, and
concurrent energetic particle bombardment (flux, particle mass, energy)
 Details of film growth on the substrate surface--e.g., substrate temperature, nucleation, interface
formation, interfacial flaw generation, energy input to the growing film, surface mobility of the
depositing adatoms, growth morphology of the film, gas entrapment, reaction with deposition
ambient (including reactive deposition processes), and changes in the film properties during
deposition
 Postdeposition processing and reactions--e.g., reaction of film surface with the ambient, thermal or
mechanical cycling, corrosion, interfacial degradation, burnishing of soft surfaces, shot peening, and
over coating ("topcoat")
Types of PVD process:
Synthesis of the coating vapor can be accomplished by any of several methods, such as electric
resistance heating or ion bombardment to vaporize an existing solid (or liquid). These and other variations
result in several PVD processes. They are grouped into three principal types: (1) vacuum evaporation, (2)
sputtering, and (3) ion plating. Table 28.2 presents a summary of these processes.

Application of PVD:
 Applications of PVD include thin decorative coatings on plastic and metal parts such as trophies,
toys, pens and pencils, watchcases, and interior trim in automobiles. The coatings are thin films of
aluminum (around 150nm) coated with clear lacquer to give a high gloss silver or chrome
appearance.
 Another use of PVD is to apply antireflection coatings of magnesium fluoride (MgF2) onto optical
lenses.
 PVD is applied in the fabrication of electronic devices, principally for depositing metal to form
electrical connections in integrated circuits.
 Finally, PVD is widely used to coat titanium nitride (TiN) onto cutting tools and plastic injection
molds for wear resistance.
Vacuum Evaporation Process:
Certain materials (mostly pure metals) can be deposited onto a substrate by first transforming them
from solid to vapor state in a vacuum and then letting them condense on the substrate surface. The setup for
the vacuum evaporation process is shown in Figure 9. The material to be deposited, called the source, is
heated to a sufficiently high temperature that it evaporates (or sublimes). Since heating is accomplished in a
vacuum, the temperature required for vaporization is significantly below the corresponding temperature
required at atmospheric pressure. Also, the absence of air in the chamber prevents oxidation of the source
material at the heating temperatures.

Fig-9
Various methods can be used to heat and vaporize the material. A container must be provided to hold
the source material before vaporization. Among the important vaporization methods are resistance heating
and electron beam bombardment. Resistance heating is the simplest technology. A refractory metal (e.g., W,
Mo) is formed into a suitable container to hold the source material. Current is applied to heat the container,
which then heats the material in contact with it. One problem with this heating method is possible alloying
between the holder and its contents, so that the deposited film becomes contaminated with the metal of the
resistance heating container. In electron beam evaporation, a stream of electrons at high velocity is directed
to bombard the surface of the source material to cause vaporization. By contrast with resistance heating,
very little energy acts to heat the container, thus minimizing contamination of the container material with the
coating.
Whatever the vaporization technique, evaporated atoms leave the source and follow straight-line
paths until they collide with other gas molecules or strike a solid surface. The vacuum inside the chamber
virtually eliminates other gas molecules, thus reducing the probability of collisions with source vapor atoms.
The substrate surface to be coated is usually positioned relative to the source so that it is the likely solid
surface on which the vapor atoms will be deposited. A mechanical manipulator is sometimes used to rotate
the substrate so that all surfaces are coated. Upon contact with the relative cool substrate surface, the energy
level of the impinging atoms is suddenly reduced to the point where they cannot remain in a vapor state;
they condense and become attached to the solid surface, forming a deposited thin film.
Sputtering Process:
If the surface of a solid (or liquid) is bombarded by atomic particles of sufficiently high energy,
individual atoms of the surface may acquire enough energy due to the collision that they are ejected from the
surface by transfer of momentum. This is the process known as sputtering. The most convenient form of
high energy particle is an ionized gas, such as argon, energized by means of an electric field to form a
plasma. As a PVD process, sputtering involves bombardment of the cathodic coating material with argon
ions (Ar+), causing surface atoms to escape and then be deposited onto a substrate, forming a thin film on
the substrate surface. The substrate must be placed close to the cathode and is usually heated to improve
bonding of the coating atoms. A typical arrangement is shown in Figure 10.
 Fig-10
Whereas vacuum evaporation is generally limited to metals, sputtering can be applied to nearly any
material—metallic and nonmetallic elements; alloys, ceramics, and polymers. Films of alloys and
compounds can be sputtered without changing their chemical compositions. Films of chemical compounds
can also be deposited by employing reactive gases that form oxides, carbides, or nitrides with the sputtered
metal. Drawbacks of sputtering PVD include (1) slow deposition rates and (2) since the ions bombarding the
surface are a gas, traces of the gas can usually be found in the coated films, and the entrapped gases
sometimes affect mechanical properties adversely.
CHEMICAL VAPOR DEPOSITION (CVD):
Chemical Vapor Deposition (CVD) is a versatile process that can be used to deposit layers of nearly
any metal, as well as nonmetallic elements, such as carbon and silicon . Compounds such as carbides,
nitrides, oxides, intermetalics, and many others also can be deposited.
A CVD reaction is controlled by these factors:
 Thermodynamic, mass transport, and kinetic considerations
 Chemistry of the reaction
 Processing parameters of temperature, pressure, and chemical activity
Principles of Chemical Vapor Deposition:
The CVD process can be defined as the deposition of a solid on a heated surface via a chemical
reaction from the vapor or gas phase. It belongs to the class of vapor-transport processes that are atomistic in
nature, that is, the deposition species are atoms or molecules, or a combination thereof. Other vapor-
transport processes include the physical vapor deposition (PVD) techniques, such as vacuum, evaporation,
sputtering, ion plating, ion-beam assist, arc, and ion implantation Unlike CVD processes, the PVD
processes do not rely on a chemical reaction in the gas phase to form the product that will be deposited.
CVD materials and Reactions:
In general, metals that are readily electroplated are not good candidates forCVD,owing to the
hazardous chemicals thatmust be used and the costs of safeguarding against them. Metals suitable for
coating by CVD include tungsten, molybdenum, titanium, vanadium, and tantalum. Chemical vapor
deposition is especially suited to the deposition of compounds, such as aluminum oxide (Al2O3), silicon
dioxide (SiO2), silicon nitride (Si3N4), titanium carbide (TiC), and titanium nitride (TiN). The commonly
used reacting gases or vapors are metallic hydrides (MHx), chlorides (MClx), fluorides (MFx), and
carbonyls (M(CO)x), where M ¼ the metal to be deposited and x is used to balance the valences in the
compound. Other gases, such as hydrogen (H2), nitrogen (N2), methane (CH4), carbon dioxide (CO2), and
ammonia (NH3) are used in some of the reactions.
 Table 1 presents some examples of CVD reactions that result in deposition of a metal or ceramic
coating onto a suitable substrate. Typical temperatures at which these reactions are carried out are also
given.

Process of Chemical vapour deposition:

Chemical vapor deposition processes are carried out in a reactor, which consists of
(1) Reactant supply system,
(2) Deposition chamber, and
(3) Recycle/ disposal system.
Although reactor configurations differ depending on the application, one possible CVD reactor is
illustrated in Figure 7. The purpose of the reactant supply system is to deliver reactants to the deposition
chamber in the proper proportions Different types of supply system are required, depending on whether the
reactants are delivered as gas, liquid, or solid (e.g., pellets, powders).

Fig-7
 The deposition chamber contains the substrates and chemical reactions that lead to deposition of
reaction products onto the substrate surfaces. Deposition occurs at elevated temperatures, and the
substratemust be heated by induction heating, radiant heat, or other means. Deposition temperatures for
different CVDreactions range from250ºC to 1950ºC (500ºF–3500ºF), so the chamber must be designed to
meet these temperature demands.
The third component of the reactor is the recycle/disposal system, whose function is to render
harmless the byproducts of the CVD reaction. This includes collection of materials that are toxic, corrosive,
and/or flammable, followed by proper processing and disposition.
Key steps followed for CVD process
1. Evaporation and transport of reagents (i.e. precursors) in the bulk gas flow region into the
reactor;, (the stages of precursors transition is shown in Fig-8)
2. Gas phase reactions of precursors in the reaction zone to produce reactive intermediates and gaseous by-
products;
3. Mass transport of reactants to the substrate surface;
4. Adsorption of the reactants on the substrate surface;
5. Surface diffusion to growth sites, nucleation and surface chemical reactions leading to film
formation;
6. Desorption and mass transport of remaining fragments of the decomposition away from the
reaction zone.

Fig-8
Typical DSC trace, illustrating four different types of transition: (I) a baseline shift caused by a glass
transition; (II) an endothermal effect caused by melting; (III) an endothermal effect caused by dissociation
of the compound; (IV) an exothermal effect caused by decomposition of the compound.
Application:
 Semiconductor and other electronic component manufacturing processes
 Coatings on tools, bearings, and other wear-resistant parts
 Optical, opto-electronic, and corrosion-resisting products
 Monolithic parts, ultrafine powders, and high-strength fibers
METAL SPRAYING:
In metal spraying adhesion is generally achieved by a mechanical "keying" action rather than inter
diffusion so a uniformly rough surface is desirable. Various abrasives may be used, flint and steel being
common, for removal of the bulk of the scale. Flame cleaning is used to remove grease and dirt and reduce
the last traces of oxide on the surface. If the spraying is being used to build up worn parts of machinery, then
further preparation may be required, including acid pickling and etching.
Spray guns are all based on the principle that a high-pressure jet of hot gas can break up molten
metal into droplets which may be carried in the gas at speeds of 200-270 m/sec (the "aerosol" principle). The
particles of molten metal should be deposited initially in the molten state but then effectively chill-frozen
such that the deposit may have the character of a casting. Metal may be supplied in the form of powder or
wire and melting may be carried out either by the gas stream itself(oxy-acetylene perhaps) or by secondary
electric arc devices.
The structure of the sprayed metal coating indicates a chill cast character and there has been some
controversy on whether the metal particles are deposited liquid and adhere by diffusion, or are deposited
solid and adhere by welding.
Zinc and aluminium are the main metals which are spray coated because of their importance in
galvanic protection. For coating of external structural work the thickness may be about 0-1 mm, and half this
value would suffice for many internal applications unless particularly corrosive industrial atmosphere were
prevalent. Other metals are used in rather specialized applications, e.g. tin for food processing equipment,
lead and nickel in chemical plant, bronze for decorative appearance.
SURFACE PREPARATION:
Surface Preparation requirement for metal spraying:
To ensure adequate bonding of thermal spray coatings, it is critical that a substrate be properly
prepared. Surfaces must be clean, and usually substrates must be roughened after cleaning by grit blasting or
some other means. Of course, the surface must remain uncontaminated by lubricants from handling
equipment or body oils from hands and arms after it is prepared. It is recommended that the prepared surface
be coated as soon as possible after preparation to prevent the possibility of contamination or surface
oxidation.
Cleaning and Degreasing:
Rust or other corrosion products; oils, grease, or other lubricants; paint; or other surface
contaminants must be removed before coating deposition is begun. They can be removed by scraping, wire
brushing, machining, grit blasting, or chemical action. Care should be taken not to embed scale and the like
in the surface when trying to remove it, particularly when using grit blasting. Solvent degreasing has been
the most common method for removal of lubricants and body oils, most conveniently with vapor degreasers.
Large parts, and parts with attached hardware that may be damaged by vapor degreasing, should be
degreased manually using the least hazardous material available. All solvents should be used only in well-
ventilated areas, by properly protected personnel who are trained in their use and who follow local
regulations for the use, care, and handling of solvents. More recently there has been a trend toward the use
of aqueous detergents and alkaline cleaners, sometimes with ultrasonic agitation, to avoid the hazards and
environmental concems of organic solvents. Additional information is available in the Section "Surface
Cleaning" in this Volume.
Surface Roughening:
Three methods of surface roughening for thermal spray are widely used: rough threading, grit
blasting, and a combination of rough threading followed by grit blasting.
Rough threading is generally used for cylindrical surfaces and with thick flame sprayed coatings.
The part to be prepared is mounted in a lathe and a single thread cut is taken. Tools for this purpose have a
60 ° to 70 ° point with a slight negative back rake. Screw feeds are approximately 0.80 to 1.25 mm (0.032 to
0.050 in.) or 0.78 to 1.26 threads/mm (20 to 32 threads/in.). The depth of the cut should vary with the screw
feed and the required coating thickness.
This technique is obviously limited to substrate sections thick enough to support the machining
without significantly reducing its strength. It is most frequently used with flame sprayed coatings and is not
recommended for thin coatings. Higher bond strengths are obtained when threading is followed by grit
blasting. When the use of cutting fluid is necessary for threading, the part must be degreased before grit
blasting or coating. Grit blasting equipment used for thermal spray should not be used for other purposes,
because dirt, paint, and lubricants contaminating the grit can be re deposited on the grit blasted surfaces.
The grit should be continuously reclassified to remove fines. The air supply to the grit blast equipment must
be clean and dry (including oil and particle filtration).
Aluminum oxide and chilled iron are the most widely used abrasive grits for thermal spray surface
preparation. However, sand, crushed steel, and silicon carbide are also used in some situations. Sand is
commonly used on large exterior structures such as bridges, towers, and piping where recovery of the grit is
impractical. Crushed steel grit, obtained commercially in hardnesses to 65 HRC, is used in preparing some
steels. Silicon carbide is used for some special applications (e.g., for very hard substrates or to minimize
contamination), but it is relatively expensive, breaks down quickly, and tends to embed in softer substrates.
MECHANICAL PROPERTIES OF SPRAYED METAL:
 The mechanical properties Most mechanical properties are measured parallel to the surface, in part
because it is easier to produce test specimens in this plane because the coatings are typically thin.
 Thee measurement of various mechanical properties of these standardized coatings may be very
useful in the selection of coatings for specific applications. Properties that may be of value include
the modulus of rupture, modulus of elasticity, and strain-to-fracture in addition to hardness.
 Coating properties are different parallel to the surface than perpendicular to the surface because of
the lamellar nature of the microstructure).
 It is frequently important to know, for example, how much strain can be imposed on a coating due to
extension or deflection of the part without cracking the coating. Cracks in a coating may not only
affect its performance, but also initiate cracks and fatigue failures in the part.

PLASMA COATING:
Plasma-arc Spraying process:
The transferred plasma-arc process adds to plasma spray the capability of substrate surface heating
and melting. Figure 7 is a schematic representation of the process. A secondary arc current is established
through the plasma and substrate that controls surface melting and depth of penetration. Several advantages
result from this direct heating: metallurgical bonding, high-density coatings, high deposition rates, and high
thicknesses per pass.
Process parameters : Coating thicknesses of 0.50 to 6.35 mm (0.020 to 0.250 in.) and widths up to 32 mm
(1.25 in.) can be made in a single pass at powder feed rates of 9 kg/h (20 lb/h). In addition, less electrical
power is required than with nontransferred arc processes. For example, for an 88% tungsten carbide, 12%
Co material, plasma spray deposition 0.30 mm (0.012in.) thick and 9.50 mm (0.375 in.) in width might
require 24 passes at 40 to 60 kW to achieve maximum coating properties. This same material can be applied,
using the transferred plasma-arc process, in one pass at approximately 2.5 kW.
 Fig. Transferred Plasma arc spraing
The method of heating and heat transfer in the transferred plasma-arc process eliminates many of the
problems related to using powders with wide particle size distributions or large particle sizes. Larger-
particle-size powders, for example in the 50-mesh range, tend to be less expensive than closely classified
325-mesh powders. Some limitations of the process should be considered for any potential application.
Because substrate heating is a part of the process, some alteration of its microstructure is inevitable.
Applications are also limited to substrates that are electrically conductive and can withstand some melting.
The transferred plasma-arc process is used in hardfacing applications such as valve seats, plowshares, oil
field components, and mining machinery.
Applications:
[Link] Resistance. One of the most important uses of thermal spray coatings is for wear resistance.
They are used to resist virtually all forms of wear,
[Link] Control. Thermal spray coatings are used in some applications to provide specific
frictional characteristics to a surface, coveting the full spectrum from low friction to high.
[Link] Resistance. Flame sprayed aluminum and zinc coatings are frequently used for corrosion
resistance on bridges, ships, and other structures.
[Link] Restoration. Thermal spray coatings are often used to restore the dimensions of a
wom part.
[Link] Applications. Plasma spray coatings, and to a more limited extent other thermal spray
coatings, are used as thermal barriers.