Phase Change Processes for Material Property Manipulation

CHAPTER 10

Mechanical Properties
Strength Toughness Hardness Ductility Brittleness Malleability Fatigue strength Corrosion Material
Composition Microstructure

Thermal processing history

Mechanical Properties ..
Composition

Property
Microstructure

Thermal process
Property Manipulation

Mechanical Properties ..
Composition
Thermal history

Microstructure

Properties

Property Manipulation

Pure metals and alloys

Pure metals like ultra-high purity copper or aluminium is used to make microelectronic circuitry However, the addition of impurities or alloying elements influences its behavior.

Pure metals and alloys

Jewelry can be made of pure gold or silver, but they are extremely soft and malleable. So to retain the shape, jewelers add copper to gold and silver. Brass which is an alloy of Cu-Zn is stronger than pure copper

How to increase mechanical properties?

Many engineering alloys can be hardened and strengthened by time induced transformation, and Temperature induced transformations These transformations occur at the crystal structure

Phase of Material
is defined as a chemically and structurally homogenous state of the material (metal alloy) A homogeneous atomic structure and composition is called a phase Alloy: brass mixture of Cu & Zn carbon steel Fe & C Components: Cu/Zn; Fe/C

Phase of Material
A phase has the following characteristics: the same structure and atomic arrangement throughout Same composition and properties A definite interface between one phase and its surrounding phase

Example
A block of ice enclosed in a vacuum chamber begins to melt and some of the water vaporizes. Here it exists in three phases: solid ice Liquid water Gaseous water Each of these phases are distinct: each has unique atomic arrangement, unique properties and definite boundary between each form called grain boundary

Phase of Material ..
A material can exist in more than one phase at a given temperature polyphase material Metals in solid state gold+silver do not form a compound two or more phases can exist in solid form Solid solution is a solid in which one element is dissolved in another and homogeneously dispersed at atomic scale

Solid Solution
Solution is a homogenous mixture of chemically distinct substances in which the atoms or molecules of one substance are uniformly dispersed throughout the other. The substance in major portions is known as the solvent & the substance in minor proportions is known as the solute. Example
Liquid solution salt in water Solid solution Cu+Ni,Gold+Silver

Solid solution
A solid solution is not a mixture. A mixture contains more than one type of phase whose characteristics are retained when the mixture is formed In contrast, a solid solution may completely dissolve in one another and do not retain their original characteristic

SOLID SOLUTION
THIS IS AN INTERSTITIAL SOLID SOLUTION WHERE SOLUTE ATOMS OCCUPY INTERSTITIAL SPACES OF HOST ATOMS (USUALLY SMALL ATOMS LIKE CARBON)

SOLID SOLUTION
SUBSTITUTIONAL SOLID SOLUTION WHERE SOLUTE ATOMS (USUALLY LARGER THAN HOST ATOMS) REPLACE SOME SOLVENT OR HOST ATOMS

Phase of Material ..
For example: in a binary alloy the micro structure can take one of the four forms:
A single solid solution Two essentially pure components Two separated solid solutions A compound

Phase of Material ..
The overall properties of a polyphase material depend upon
No. of phases present Relative amount of each phase Composition & microstructure of each phase Size & distribution of the phases in the microstructure These characteristics are a function of temperature phase diagrams

Phase Diagram
A graphical representation of phases and composition as a function of temperature, at equilibrium
Liquid metal solution Temperature Liquid + Solid metal solution Solid metal solution Composition 100 % 0

Gold 0 Silver 100

Phase Diagram
A phase equilibrium diagram is a graph showing phase relationships that occur in a metal alloy as it slowly cools from the molten state Equilibrium is said to exist when enough time is allowed for everything that wants to occur

Phase Diagram ..
An equilibrium diagram or constitutional diagram Relationship between temperature and constituents for all possible compositions Transformations which may occur in solid state Number of phases present, their composition and amount

MELTING POINT
A PURE METAL WILL HAVE A SINGLE MELTING POINT An alloy will have a melting temperature range. In this range, the metal will be part solid and part liquid

This microstructure is for a given composition of the alloy

Microstructure of a completely soluble metal (solute) in another metal(solvent) alloy Only one phase is present

Microstructure of partial solid solubility

Figure shows two phases existing. The second phase is formed at the grain boundary of the first

This microstructure is for a given composition of the alloy

Cooling Curves
Liquid (molten) state to solid state Temp. vs time Pure metal: melting point one temp. (BC) Slope AB & CD specific heat

A Temperature

Liquid Metal B C Solid Metal

D Time

Cooling Curves ..
Alloy: melting point not unique temp. BC range of temp.

A' Temperature B'

Liquid Metal L+S Metal C' E' D' Time Solid Metal

Equilibrium Diagram
for two metals which are completely soluble in liquid & solid phases For each composition one cooling curve Plot all cooling curves on one diagram phase diagram

Equilibrium Diagram ..
Temperature Liquid metal solution Liquidus B Liquid + Solid A metal solution Solid metal solution 25 50 50 75 100 % 0

Solidus

Gold 0 Silver 100

FOR 100% SILVER

A
FOR (100-C)% SILVER AND C% GOLD
A

P
Q

B
FOR 100% GOLD

The boundary APB is called liquidus and represents temperature beyond which composition will be entirely in liquid state

the the the the

The boundary AQB is called solidus and represents temperature below which composition will be entirely in solid state

the the the the

Equilibrium Diagram ..
TH B TB F D TD TA G A Temperature Liquid 1 phase H Liquidus Liquid + Solid 2 phases C Solidus Line representing an alloy containing 20 % gold 80% silver

Solid 1 phase

Gold 0 10 20 30 40 50 Silver 100 50 80 Composition percentage by weight

Lever Rule
Used to calculate % of each phase present in a two phase region. For example at temperature TD:

DE %Liquid present = 100 FE FD %Solid present = 100 FE

Two Component Eutectic System

Two components A and B TmA melting point of A TmB melting point of B Mix of A+B solidifies over a range of T Some composition constant melting point behave as a pure element

eutectic point/Temperature TE

Two Component Eutectic System

TmA L+S(A) TE
Eutectic point Solidous

Liquidous

TmB

L+S(B)

S(A+B) B

Eutectic Point
This is the composition for which there is no freezing range It is a composition with a single melting temperature, just as a perfectly pure crystal would have An alloy with a eutectic composition has the lowest melting temperature

TE
EUTECTIC TEMP

TE

Two Component Eutectic System

Solid Solution of B in A mostly A Solid Solution of A in B

Two Component Eutectic System

TmA L+S() TE
Eutectic point

Liquidous

TmB

L+S()
Solidous

S(+) A B

Alloys that exceed solubility limit

Alloys containing between 2% to 19% Sn will solidify to a single solid solution . However, as the alloy continus to cool, a solid state reaction occurs, permitting a second phase ( ) to precipate from the original phase. is a solid solution of tin in lead and is a solid solution of lead in tin However, the solubility of tin in lead is limited. At 0OC, only 2% Sn can dissolve in Pb. The maximum +L solubility of Sn in Pb is 19% at OC 183 Any alloy between 2and 19% Sn when cools past the solvus curve, the solubility limit is exceeded and a small amount of forms.

AT EUTECTIC POINT

L61.9% of Sn 19%Sn + 97.5%Sn

EUTECTIC

61.9 % Pb Sn

EUTECTIC

HYPOEUTECTIC ANY COMPOSITION BETWEEN 19% AND 61.9% Sn IS CALLED HYPOEUTECTIC ALLOY HERE ANY COMPOSITION WITHIN THE RANGE WHEN COOLED WILL BEGIN TO SOLIDIFY AT THE LIQUIDUS TEMP PRODUCING SOLID
ON FURTHER COOLING COMPLETE SOLIDIFICATION OCCURS AFTER EUTECTIC REACTION

+L 61.9% + Pb

+L

Sn

EUTECTIC

HYPEREUTECTIC ANY COMPOSITION BETWEEN 61.9% AND 97.5% Sn IS CALLED HYPEREUTECTIC ALLOY HERE ANY COMPOSITION WITHIN THE RANGE WHEN COOLED WILL BEGIN TO SOLIDIFY AT THE LIQUIDUS TEMP PRODUCING SOLID
ON FURTHER COOLING COMPLETE SOLIDIFICATION OCCURS AFTER EUTECTIC REACTION

+L 61.9% + Pb

+L

Sn

EUTECTICS AND MATERIAL PROCESSING

EAMPLE 1 IF WE WANT TO JOIN TWO COPPER PIPES, THEN WE CAN INTRODUCE LOW MELTING POINT EUTECTIC ALLOYS (LIKE Pb-Sn) BETWEEN THE JOINTS OF THE TWO PIPES. THEN ONCE WE HEAT THE COPPER PIPES ABOVE THE EUTECTIC TEMPERATURE, THE ALLOY WILL MELT WHICH WHEN COOLED AND SOLIDIFIED WILL JOIN THE COPPER PIPES EXAMPLE 2 MANY CASTING ALLOYS ARE BASED ON EUTECTIC ALLOYS;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;WHY ? HINT: TO REDUCE ENERGY COST IS CAST IRON AN EUTECTIC ALLOY?????????????

ALLOTROPES OF PURE IRON

LIQUID 1538 -IRON (BCC) 1400 -IRON (FCC)

910

-IRON (BCC)

IronIron-Carbon Equilibrium Diagram

Basis of all ferrous materials alloys of Fe & C Iron & steel Properties & property change processes Fe+C Alloys Steel: <2% C Cast Iron: 2-6.67% C >6.67% C: Fe3C not metal (called cementite)

IronIron-Carbon Equilibrium Diagram

0 to 6.7 % C Pure Iron at diff. Temp. >6.7% not Delta Iron useful Austenite or In solid state Gamma Iron Fe+C takes Ferrite or Alpha different forms iron BCC

IronIron-Carbon Equilibrium Diagram

Composit Property ion Austenite Carbon+ Only at high T iron Good formability non-magnetic Ferrite 0.022%C Soft & ductile (max) + ferrite is stable iron only at high temp & is of no significance Phase

IronIron-Carbon Equilibrium Diagram

Very hard & brittle Very little resistance to shock Pearlite Cementite Not a phase by + ferrite itself (a lamellar considerably structure) stronger than ferrite Cementite 6.67%C +Fe (Fe3C)

Fe 100% C 0%

CARBON PRESENT IN STEEL IS IN FORM OF CEMENTITE (FE3C) CONTAINING 6.67% OF CARBON. BEYOND 6.67% CARBON IN STEEL MAKES THE ALLOY VERY BRITTLE, THERFORE MAKING IT USELESS FOR ANY APPLICATION. 93.33 6.67 ( 100% CEMENTITE)

HENCE WE WILL INVESTIGATE ONLY UPTO 6.67% CARBON. SO Fe-C Dg CAN BE ALTERNATIVELY CALLED Fe-Fe3C Dg

TEMPERATURE

SOLUBILITY OF CARBON (OR CEMENTITE) IN IRON

-IRON (BCC) 1148OC -IRON (AUSTENITE) -IRON (-FERRITE) 727OC A B C

MAX SOLUBILITY OF CARBON IN AUSTENITE 2.11% (PT C) AT 1148OC MAX SOLUBILITY OF CARBON IN BCC IRON ( FERRITE) 0.022% (Pt A) AT 727OC MAX SOLUBILITY OF CARBON IN BCC IRON ( IRON) 0.09%

-IRON (BCC) 1148OC -IRON (AUSTENITE) -IRON (-FERRITE) 727OC

AUSTENITE: SOLID SOLUTION OF IRON AND CEMENTITE. IT HAS GOOD FORMABILITY AND IS NON-MAGNETIC FERRITE: SOLID SOLUTION OF -IRON AND CEMENTITE. IT IS RELATIVELY SOFT, DUCTILE AND MAGNETIC AT ROOM TEMPERATURE

EUTECTOID REACTION
EUTECTOID IS A SOLID STATE REACTION IN WHICH ONE SOLID PHASE TRANSFORMS TO TWO OTHER SOLID PHASES 727OC 0.8% C

S1

S2+S3

HEATING AN ALLOY OF COMPOSITION GREATER THAN 0.8% CARBON ABOVE 727OC WE GET AUSTENITE COOLING THE SAME AUSTENITE TO 727OC, THE EUTECTOD REACTION BEGINS

EUTECTOID REACTION
THE EUTECTOID COMPOSITION OF FERRITE AND CEMENTITE IS CALLED AS PEARLITE PEARLITE CONSISTS OF ALTERNATE THIN LAMINATES OF CEMENTITE AND FERRITE

(0.8% C)(0.022%C)+Fe3C(6.67%) THE IRON IN AUSTENITE DIFFUSES TO AND CARBON TO Fe3C (TRANSFORMATION POSSIBLE WHEN COOLING IS SLOW)

IronIron-Carbon Equilibrium Diagram

IronIron-Carbon Equilibrium Diagram

1495 1394 1150 Temperature C 912 G A3 Ferrite + 727 100 P 0.022 % a Al
Eutectoid

J N 0.17 % Solidus c
3 2.11 %

Austenite (solid solution of carbon in gamma iron) A CM

1 Austenite

b
0.8 %

Austenite + Cementite

S Pearlite + Cementite Hypereutectoid steel

Ferrite+Pearlite

Hypoeutectoid
steel

0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 2.00 2.20 Carbon %

IronIron-Carbon Equilibrium Diagram

1150 912 G A 727 100
3

A u s te n ite (s o lid s o lu tio n o f c a rb o n in g a m m a iro n ) a

1

b
l

P 0 .0 2 2 %

F e r rite + A u s te n ite

CM

S
0 .8 % E u te c to id

F e r r ite + P e a rlite
H y p o e u te c to id

s te e l

0 .2 0 0 .4 0

0 .6 0

0 .8 0

COOLING FROM a
WHEN A HPPOEUTECTOID STEEL COOLS FROM THE AUSTENITE STATE, PRIMARY FERRITES NUCLEATES AND GROWS AROUND THE GRAIN BOUNDARY OF AUTENITE AT 727OC, THE REMAINING AUSTENITE WHICH IS SURROUNDED BY FERRITE HAS INCREASED ITS CARBON % TO 0.8% WHEREBY EUTECTOID REACTION OCCURS AND THE REMIANING AUSTENITE CONVERTS TO PEARLITE

IronIron-Carbon Equilibrium Diagram

At S 0.8% C Austenite breaks into ferrite and cementite pearlite a lamellar structure Eutectoid temperature/ Composition/transformation <0.8%C pearlite+Ferrite Hypoeutectoid >0.8%C pearlite+cementite Hypereutectoid

IronIron-Carbon Equilibrium Diagram

Austenite (solid solution of carbon in G gamma iron) Eutectoid A CM A3 a b Austenite + 1 Ferrite + Cementite Austenite A l S P 0.022 % 0.8 % Ferrite+Pearlite Pearlite + Cementite Hypoeutectoid steel Hypereutectoid steel

912

727 100

0.20 0.40 0.60 0.80 1.00 1.20 1.40 Carbon %

IronIron-Carbon Equilibrium Diagram

S o lid u s 1150 912 b 727 100 S
0 .8 % P e a rlite + C e m e n tite H y p e re u te c to id s te e l
2 .1 1 %

A u s te n ite A CM

c
3

A u s te n ite + C e m e n tite

0 .8 0 1 .0 0 1 .2 0 1 .4 0 1 .6 0 1 .8 0

2 .0 0 2 .2 0

Cooling from c
WHEN A HYPEREUTECTOID STEEL COOLS FROM AUSENITE PHASE, THE PRIMARY PHASE CEMENTITE FORMS AT THE AUSTENITE GRAIN BOUNDARY. AT 727OC, THE REMAINING AUSTENITE WHICH IS SURROUNDED BY HARD AND BRITTLE CEMENTITE UNDERGOES EUTECTOID REACTION AND CONVERTS TO PEARLITE.

CONTROLLING EUTECTOID REACTION

AS CARBON CONTENT OF STEEL INCREASES TO 0.8%, THE AMOUNTS OF CEMENTITE AND PEARLITE INCREASES, THUS INCREASING THE STRENGTH WHEN CARBON CONTENT IS TOO HIGH (>>>>0.8%) WILL RESULT IN DECREASE OF PROPERTY. BY INCREASING THE COOLING RATE (FASTER COOLING), FROM THE AUSTENITE STATE, A METASTABLE PHASE CALLED MARTENSITE IS FORMED. MARTENSITE IS BRITTLE. MARTENSITE CANT BE OBSERVED IN EQUILIBRIUM DIAGRAM AS IT DEPENDS ON TIME

EUTECTIC REACTION

LIQUID LIQUID
+LIQUID +LIQUID

1148 C

O 1148OC

Fe3C Fe3C +LIQUID +LIQUID

AUSTENITE+Fe AUSTENITE+Fe3C 3C

4.3%C 4.3%C

THE COMPOSITION AT WHICH THE ALLOY HAS THE LOWEST MELTING POINT

Heat Treatment Processes

Required to obtain the required mechanical & physical properties Ex. steel can be made soft & ductile, hard & wear resistant through heat treatment.

Annealing
Heating the steel to a temperature at or near the critical temp. range Cooling it at a predetermined rate, & employing usually a relatively slow cooling, a holding period,& a controlled cooling Annealing is done for 1. Reducing hardness, 2. Improving machinability, 3. Removing internal stresses etc.

Here the temp is raised to A3 and Acm where it converts to austenite for steels or austenite-cementite for cast iron Then it is held at that temp for some period Followed by slow cooling (usually furnace cooling)

Where annealing is required?

Steel products made by cold rolling or drawing work harden and become brittle. The steel can be softened by annealing. The slow cooling transforms austenite to ferrite and pearlite Hardened workpiece are annealed to increase their machinability because the ferrite-pearlite combination have a good machinable structure Internal stresses are formed from cold working, welding or some fabrication process. Such parts are annealed to remove internal stresses. At high temp, the distorted and stressed lattice atoms rearrange to form neutral or undistorted grains

Normalizing
Process is very similar to annealing Here the steel is heated to the fully austenite region (38-60oC above Ac3) Soaked at that temp for some time Air cooled to room temp

Normalizing
The rate of cooling in normalizing is higher than annealing, therefore the part has more hardness and less ductility to that of an annealed part This is usually performed to give uniform grain size distribution. For example, castings made from alloys often locally cool at different rates, resulting in grain size difference in the same part Also workability of steel is improved

Hardening
Hardening of steel requires the change from BCC to FCC structure This process is accomplished by first heating the steel to a temperature above the critical temperature & keeping at this temperature long enough to completely transform the steel to austenite. Then it is cooled at a rapid rate by quenching in water,oil or any other quenching medium. By rapidly cooling, the carbon gets trapped in the crystal structure

Austenite 727oC Rapid cooling MORE MARTENSITE WITH FASTER COOLING

Martensite

MARTENSITE is a non-equilibrium constituent. It is hard, strong and brittle

Hardening. Hardening.
The ability of steel to become hardened to specified depth below its surface is known as hardenability. It tells us the ease with which steel transforms to a hardened structure

Case Hardening

The oldest method of producing a hard surface on steel is case hardening or carburising

Case Hardening or Carburizing

Case hardening process consists of heating steel parts in gas tight cast iron or alloy steel boxes packed with charcoal The oxygen within the boxes combine with carbon from charcoal to form carbon mono oxide. In contact with heated steel CO give up carbon, which diffuses into the surface. The oxygen is freed to combine with more C from charcoal. Milling cutters are case hardened to impart the hardness to the surfaces of the cutting edges.
SURFACE HARDENING TECHNIQUE

Tempering
The tempering process consists of Heating the hardened steel to a temp below the critical temp. exact temperatures at which tempering should be done depends upon the purpose. Holding it at that temp for a specified time. Slow cooling Tempering is done at lower temp so all the hardness is not lost.

WHY TEMPERING IS REQUIRED

Quench hardened steels form a martensitic structure, which are very brittle. They are so brittle, that on slight impact or bending will cause fracture. So tempering is done to improve the toughness So some of the hardness is sacrificed to improve toughness and ductility

Strain Hardening or Work Hardening

Increase in hardness, yield point or tensile strength when material is subjected to plastic deformation is known as strain hardening It is important while carrying out metal forming operations.

Recovery, Recrystallization and Grain growth

When material is plastically deformed, the effective grain size is distorted and reduced After deformation, when this load is released, the rigid crystal structure will hamper the elastic recovery and internal stresses are developed The process os restoring the original grain geometry relieved of internal stresses is called .

FORGING

ROLLING

Note
Atoms along grain boundary are packed less efficiently and are more disordered. As a result they have much higher strength than those outside During deformation, grain boundary remain intact, but strength increases because of entanglement of dislocation with grain boundary

Recovery
The original cold worked structure consists of deformed grains and a large number of tangled dislocations Recovery is a low temp. heat treatment processes in which the additional thermal energy moves the dislocations from the grain boundary and rearranges them. But the number of dislocations remain the same Relieves some of the internal stress obtained earlier from cold working It is the partial restoration of original properties: strength is slightly reduced & ductility is improved slightly. This is because the number of dislocations still remain the same. No microstructure changes happen

Recrystalization
Temp at which new grains are formed is known as recrystalization temp & the process is known as recrystalization. Here, most of the dislocations are eliminated, therefore the recrysatllized metal has low strength but high ductility Recrystallization temperature melting temperature is not fixed unlike

Recrystalization.. Recrystalization..
Recrystalization temp of some common metals: Aluminum 1500C Magnesium 1500C Iron----------- 4500C Copper ------2000C Gold --------2000C Lead -------- below room temp (-4oC)

Important Points
Recrystalization is a thermally activated mechanism, which occurs more rapidly at higher temperatures. Pure metal recrystalizes at a lower temp than impure one while other things are equal. This is owing to the fact that impurities lower the mobility of dislocations. For a metal of given purity the greater the degree of cold work the more readily recrystalization takes place.

Grain Growth
Occurs when temp exceeds recrystalization temp New fine grains formed from recrystallization grow in size in this scenario This growth is the result of the tendency to return to more stable & larger state. Example: formation of larger bubbles from the small bubbles of soap Grain growth has very little application

Hot and cold working

The concept of recrystallization temperature defines the boundary between hot and cold working If we conduct deformation (shaping) of a material above the recrystallization temperature, we refer to it as hot working If we conduct deformation (shaping) of a material below the recrystallization temperature, we refer to it as hot working

IRON (Fe) CAN BE COLD WORKED AT ROOM TEMPERATURE NOT LEAD (Pb) OR TIN (Sn)---------??? TUNGSTEN (W) DEFORMED AT 1000OC IS COLD WORKING

Hot Working
Several operations like forging, hot rolling etc are al performed at elevated temperatures so as to prevent the formation of distorted grains that will harden the component It is the process of working (plastic deformation) above recrystalization temp. Both recrystallization and deformation simultaneously occur. The distorted grain structure and strain hardening during plastic deformation is continuously eliminated from recrystallization Since strain hardening is eliminated, the amount of plastic deformation possible is almost unlimited (A very thick plate can be reduced to a thin sheet)

Advantages
Because of high temp, the strength of the metal is low. Hence less force required to shape the metal Impurities in the form of inclusions are broken up & broken up & distributed throughout the metal Ductility & resistance to impact are improved Blowholes & porosity are eliminated by welding action at high temp.

Limitations
High temp heating facilities are required which increases investment Poor dimensional tolerance & surface finish because oxygen reacts with the metal at high temperature forming oxides on the surface (oxidation). Hot worked steels undergo a chemical treatment called pickling to dissolve the oxide scale. Due to scaling & oxidation there is heavy material loss.

Cold Working
Working below recrystalization temp is known as cold working ADVANTAGES: 1. NO MATERIAL LOSS 2.SURFACE FINISH IS EXCELLENT 3. STRENGTH & HARDNESS OF MATERIAL IS INCREASED (Strain hardening is observed)

Cold Working
Disadvantages Large Forces Are Required For Deformation (So high capacity press is required) Only Ductile Material Can Be Cold Worked Tooling Costs Are High Subsequent Heat Treatment Is Required To Relieve The Internal Stresses Which Adds Cost.