V.J.T.I.

Presented
By
Dr. Walmik Sadashiv Rathod

Department of Mechanical Engineering,

V. J. T. I., Matunga, Mumbai-400019

Contact Numbers:
Cell - # 91 – 9892201145 Office - # 91 - 22 - 2419 8229

wsrathod@vjti.org.in

wsrathod@me.vjti.ac.in

Venue: GOOGLE MEET

Monday 26th, Oct-2020.

 Many reactions and processes that are important
in the treatment of materials rely on the transfer
of mass either within a specific solid (ordinarily
on a microscopic level) or from a liquid, a gas, or
another solid phase. This is necessarily
accomplished by diffusion, the phenomenon of
material transport by atomic motion.
 The mechanism of diffusion coatings generally can be described in
the following ways:
There initially must be higher concentration of the material to
be diffused into the substrate, and then a translocation of the
atoms occurs from the region with higher concentration into the
region with lower concentration.Thus,diffusion results in the
equalizing and stabilizing of material concentration .
 The different types of diffusion are
1. Self diffusion
2. Inter diffusion
3. Volume diffusion
4. Grain boundary diffusion
5. Surface diffusion
 Diffusion Coating is a process based on the diffusion saturation of the surface
layers of objects made of metals and alloys of various metals.

 It is used to impart special physicochemical and mechanical properties to metal

articles.

 A distinction is made among the following operations, depending on the diffusing

element: aluminizing, diffusion chrome plating, molybdenization, manganizing,
chrome calorization, and chrome-titanium plating.

 Diffusion saturation is possible from various phases: solid, gaseous, vapor, and liquid.

 Any process whereby a base metal or alloy is either (1) coated with another metal or
alloy and heated to a sufficient temperature in a suitable environment or (2) exposed to
a gaseous or liquid medium containing the other metal or alloy, thus causing diffusion
of the coating or of the other metal or alloy into the base metal with resultant changes
in the composition and properties of its surface is termed as ‘diffusion coating’.
 Diffusion saturation is possible from various phases: solid,
gaseous, vapor, and liquid.

 Any process whereby a base metal or alloy is either (1)

coated with another metal or alloy and heated to a
sufficient temperature in a suitable environment or (2)
exposed to a gaseous or liquid medium containing the
other metal or alloy, thus causing diffusion of the coating
or of the other metal or alloy into the base metal with
resultant changes in the composition and properties of its
surface is termed as ‘diffusion coating’.
 A diffusion layer 10 microns to 3 mm thick may be produced by diffusion coating.

 The diffusion processes make possible-

 an increase in the resistance of alloys to oxidation (for example, calorized steel is oxidation-
resistant up to900°C), abrasion (for example, chromium-
plated U12 steel is six times more abrasion resistant than the base metal),

 heat shock,

 rapid temperature changes,

 high corrosion and acid resistance, as well as the improvement of other properties of
metals and alloys.

 high heat resistance

 high wear resistance

 high hardness
 With low carbon steel, the surface can be enriched by diffusion of C or N into surface.
 The following thermal treatment processes come under diffusion coating-
 Carburizing
Heat steel to austenitic range (850-950 ºC) in a carbon rich environment, then quench and
temper
Take care with carbon steels as surface will decarburize

 Nitriding
Nitrogen diffusion into steels occurs around 500-560 ºC to form a thin hard surface
Good for Cr, V, W, and Mo steels. Will embrittle surface of Aluminum.

 Metal Diffusion
Chromizing – Chromium diffuses into surface to form corrosion resistant layer.

Aluminizing
Used to increase the high temperature corrosion resistance of steels and superalloys
1. Metal Bonding – Galvanizing, Welding, Brazing,
Soldering
2. Homogenising treatment
3. Recovery and Recrystallization
4. Phase change
5. Powder Metallurgy
6. Oxidation of metals
7. Surface treatment of metals
 Fick's laws of diffusion describe diffusion and can
be used to solve for the diffusion coefficient, D. They
were derived by Adolf Fick in the year 1855.
Fick's first law relates the diffusive flux to the
concentration under the assumption of steady state. It
postulates that the flux goes from regions of high
concentration to regions of low concentration, with a
magnitude that is proportional to the concentration
gradient (spatial derivative).
 In one (spatial) dimension, the law is

  
J  D 
 x 

Where
J = diffusion flux (amount of substance per unit area per unit

time) (mol / m2 sec). J measures the amount of substance that

will flow through a small area during a small time interval.

D = diffusion coefficient or diffusivity ( m2/sec )
ϕ = concentration ( mol/m3 )
x = position ( m )
         
2
    D     D  2 
t x   x    x 

 Rate of accumulation of diffusing material at a point

t
 Saturation from the solid phase is used with iron, nickel, cobalt, titanium, and other metals.
 In this case, diffusion coating is performed using various refractory metals, including molybdenu
m, tungsten, niobium, and uranium, whose
vapor pressure is lower than the vapor pressure of the basic metal.
 The process is performed in a hermetically sealed container, in which the parts to be treated are
covered with the powdered metal and heated either under a vacuum
or in an inert gas atmosphere at 1000°-1500° C.
 Saturation from the vapor phase is used for alloys based on iron, nickel, molybdenum, and titani
um with elements that have higher vapor pressures than the metal to be saturated, such
as zinc, aluminum, chromium, and titanium.
 The process is performed in hermetically sealed containers under a vacuum of 10 1~10−2 newton
per sq m (N/m2), or 101-10−4 mm of mercury (mm Hg), and at 850°-
1600°C, by the contactor noncontact method.
 In the former case, the vapor phase forms because of the sublimation of the metal and is genera
ted near the contact locations between the powdered or granular metal and the surface being pr
ocessed.
 In the
second case, generation of the vapor phase takes place at some distance from the surface.
 Saturation from the liquid phase is used in calorization and chrome, zinc,
and copper plating.

 The process takes place in tank furnaces, in which the melt of the diffusing
metal or its salt interacts with the surface of the objects being treated at
800°-1300° C.

 This method is also used for complex diffusion coating, such as chrome
calorization and chrome-titanium and chrome-nickel plating.
 Saturation from the gaseous phase is performed during diffusion coating of
various metals with aluminum, chromium, manganese, molybdenum,
tungsten, niobium, and titanium.

 The diffusion of the metal is preceded by the reactions of gaseous chemical

compounds of the diffusing element with the basic metal.

 The gas phase consists of the halides of the diffusing metals. Gaseous
saturation is performed in muffle furnaces or in specially designed furnaces
at 700°-1000° C.

 The gaseous phase may be generated at a distance from the surface being
saturated (noncontact method), as well as in the contact zone of the source
of the active phase and the metal surface (contact method).
 Various diffusion coating processes are:
 1) Calorizing
 2) Chromizing
 3) Siliconizing
 4) Boron diffusion
 The process of alloying steel with aluminium by diffusion is called
calorizing. The aluminium diffusion gives a dense film of aluminium
oxide (Al2O3) which provides reliable protection against oxidation
and corrosion.
 Calorizing is the diffusion of aluminium into the surface of a base
metal through high temperature vapors. The types of metals that can
be calorized include all types of wrought and cast steels (i.e. plain
carbon and low alloy grades, ferritic and austenitic steels, highly
alloyed nickel-chromium steels etc.).
 The reason aluminum is used to form the alloy is because it is very
corrosion resistant itself. When oxygen is present, aluminum reacts
to form an aluminum oxide layer, which is chemically bound to the
surface and seals the core aluminum from any further reaction..
Therefore, diffusing aluminum into a base metal increases its
corrosion resistance.
 The steel parts are packed in an airtight vessel called
retort. with a mixture of aluminium or ferroaluminium
powder, aluminium oxide and small amount of
ammonium chloride (0.5 to 2.0%). The retort heated to a
temperature range from 950° to 1000°C. It is held at a
constant temperature for 3 to 16 hours and then cooled
upto the room temperature.
 The aluminum is in its liquid phase and diffuses into the
surface of the metal and forms an alloy with
the substrate. This alloy usually contains a minimum of
20 percent aluminum.
 After cooling additional secondary operations are
performed as needed. This process ensures uniform
alloy protection over the entire surface of the base metal.
 (Steel Parts + Aluminium (25 % to 50 %)
+ Ammonium Chloride (0.5 to 2 %)
+ Aluminium oxide (25-75 %)

3 to 16 Hours
~950-1000

b) Holding
Temperature °C

a) Heating (c) Cooling

Time
NH4Cl  NH3 + HCl

6HCl + 2Al  2AlCl3 + 3H2

Fe + AlCl3  FeCl3 + Al(atomic) (on

steel surface)

Atomic aluminium diffuses into the iron. Calorizing

is sometimes
followed by diffusion annealing at 900° to 1000° C to
reduce the brittleness of the calorized layer.
●The process of spraying a layer of aluminium on the
surface of the steel is called as metallization.

● In this process work is heated to a temperature range

from 200° to 250° C and aluminium is sprayed on its
surface by an oxyacetylene spraying device. Heating of
the work is carried out by high frequency induction. The
surface layer obtained by this process will be from 0.015
to 0.025 mm. It is rapid process.

● This process is followed by diffusion annealing

(homogenization) at 900°-1000° C. prior to annealing
work is covered with a paste consisting of 48% silvery
graphite, 30% quartz, 20% clay and 2% ammonium
chloride.
 The purpose of the calorizing process is to improve the base
metal’s heat and corrosion resistance by providing a protective diffusion layer
of aluminum alloyed with the base metal at the surface. This layer remains
effective at all temperatures up to the melting point of the base metal. Since
the layer created is an alloy with the base metal, the layer cannot be
removed without a machining process.[
 The protective diffusion layer provides the following corrosion protection
properties:[
Sulfidation Resistance – protection from hydrogen sulfide,
hyposulfurous, and sulfurous acid attack
Oxidation Resistance – aluminum oxide forms stable coating
Carburization Resistance – resists carbon diffusion
Hydrogen Permeation – reduces rate of hydrogen diffusion
 Though corrosion protection properties are gained, the chemicals and gases
that typically corrode aluminum are not resisted. Therefore, alonized
materials should not be used where condensation from gas will occur due to
low enough temperature.
● It gives high heat resistance (at temperatures upto
850°-900°C) because of dense film of aluminium oxide
(Al2O3) forms on the surface of steel.
● Protects metal against oxidation.
● It gives high corrosion resistance.
● The aluminium penetration layer ranges from 0.2 to 1
mm.
 The process is useful in manufacturing of fire grates of
gas generator, components of ladles, valves and other
parts operating at high temperatures.
 Calorized material is used most commonly in tubing and
piping utilized in corrosive environments. These types of
tubing and piping include furnace tubes, reformer
tubes, heat exchanger tubes, waste gas heater tubes,
line pipe and down hole tubes for wells and production
vessels, sulphur condensers and piping used in oil and
chemical production and power generation and wrought
metal products, bars, rods, plates and sheets, panels,
water well panels, and wire screens and metal castings
by adding aluminum or aluminum and silicon corrosion
and erosion preventive diffusion coatings.
 Chromising (or chromizing) is a surface
treatment carried out at elevated temperatures
in which an alloy is formed by the inward
diffusion of chromium into the base metal.
 The process is not restricted to ferrous materials
and may be applied to nickel, cobalt,
molybdenum and tungsten to improve corrosion
resistance and heat resistance.
 The most widely used chromizing method is pack
chromizing.
 In this method, workpiece (generally steel) is placed
in a mixture of 50% ferro-chromium, 49%
aluminium oxide and 1% ammonium chloride.
 The steel parts are heated to a temperature range
from 1000° to 1050° C.
 Parts are held at this constant temperature.
 NH4Cl NH3 + HCl
 2HCl + Cr H2 + CrCl2
 Fe + CrCl2 FeCl2 + Cr (atomic)
 (Parts + 50 % Ferro chromium
+ 49 % Aluminum Oxide
+ 1 % Ammonium Chloride)

12-15 Hours
1000°C
(b) Holding
Temperature, °C

a) Heating (c) Cooling

Time
 Chromising can protect components from corrosion,
wear, abrasion and oxidation in engineering
environments.
 Chromide diffusion coatings are still widely applied
to hot section industrial gas turbine blades and
vanes to protect them against high temperature
oxidation and hot corrosion.
 A wide range of industrial components such as
chain pins, sprags, levers, rods and locators are
chromized.
 Steels with a carbon content greater than 0.3% can
form a hard dense diffused Chromium Carbide
surface layer which has high hardness and
excellent wear resistance.
 Chromizing process is a superior method of protection for the exposed surfaces
of critical boiler components in the aggressive environment of a recovery
furnace.
 Chromizing has proven capable of imparting a resistance to oxidation and
sulfidation attacks that exceeds that of any other method of protection.
 In addition the unique properties of the chromium enriched surface layer render
it immune to many of the problems which have plagued the other protective
systems, such as deballing and spalling observed in many coatings. The
chrome layer is not porous and will not flake off as it is a diffusion. Chromized
parts are much less susceptible to thermal fatigue.
 Chromized high carbon steels have hardness of 1200-1300 VPN.
 The chromizing of steels containing over 0.3 or 0.4 % carbon increases
hardness and wear resistance.
 Increased corrosion resistance in such media as fresh water, sea water and
nitric acid.
Materials Properties Imparted by Chromizing
Low carbon steels Oxidation resistance to 650o
C; corrosion resistance
similar to ferritic stainless steel

Medium carbon steels Light wear and corrosion resistance

High carbon steels Wear resistance and corrosion resistance

Stainless steels Wear resistance and corrosion resistance

Nickel & Cobalt base super alloys: Corrosion and erosion resistance
 Diffusion chromizing is classified, according to its
application, into two types: anti-corrosion and surface
hardening.
 Anti-corrosion chromizing is applicable to alloys
containing carbon in amounts of less than 0.2 wt% in
order to enhance their corrosion resistance and high
temperature oxidation resistance.
 Such properties are exhibited by solution-type
chromized layers, consisting of a solid solution of Cr in
α-iron, obtained on surfaces of iron or low-carbon steel.
 Their 0t hickness is usually 0.15 mm, and their hardness
the order of 200 HV.
 This process is also known as ihrigizing, is the
impregnation of steel with silicon. The
siliconizing process is carried out with help of
solid or gas medium.
• In this process, steel parts are heated with solid medium which
contains 50 to 95 % silicon, 20 % fireclay and 2.5 % AlCL
• Steel parts are heated to a temperature range from 950° to
1100° C.
• The parts are in this temperature range for 2 to 24 hours.
• The case depth obtained is from 0.2 to 0.3 mm.
• The siliconized layer is a solid solution of silicon in α-iron
• A layer of pearlite is often found under this case.
• The solid siliconizing is rarely is rarely used.
 (Part + 50-95 % Silicon
+ 20 % fireclay
+ 2-5 % Aluminium Chloride)

2 to 24 Hours
1100°
Temperature °C

(b) Holding

(a) Heating (c) Cooling

Time
 In this method steel parts heated in the
atmosphere of gaseous silicon tetrachloride
(SiCl4) obtained by passing chlorine through a
reaction chamber containing the ferrosilicon or
silicon carbide. The working temperature 950-
1000Cand then cooled to room temperature.
The case of steel parts contains 14-15% silicon.
 [Steel Parts + SiCl4]

1000° 2-5 Hours

(b) Holding
Temperature °C

(a) Heating (c) Cooling

Time
 Steel surfaces saturated with boron acquires a very high
hardness, wear resistance and corrosion resistance in
various media.
 There are 3 types of boron diffusion processes.
1. Solid Boron Saturation
2. Liquid Boron Saturation
3. Gas Boron Saturation
 [Steel Parts + Molten Borax (Na2B2O7)]

2-6 Hours
950°
(b) Holding
Temperature °C

(a) Heating (c) Cooling

Time