Solidification of pure metal and alloys

solidification is the most important phase transformation

Coz almost metal/alloy most undergo this transformation before becoming useful objects.

Solidification involve solid-liquid phase transformation E.g casting process Solidification in welding process solidification steps nucleation-formation stable nuclei in melt Growth of nuclei into crystal Formation of grain structure

a) Nucleation of crystals, b) crystal growth, c) irregular grains form as crystals grow together, d) grain boundaries as seen in a microscope.

Solidification in cast metal

3 zone structure of an ingot

chill zone structure consists of many

small roughly equiaxed grains nucleation occurs from vary many site along mold wall fine grain structure

Columnar Zone
consist dendrites structure Some of the dendrites oriented perpendicular to wall/dendrite axes at an angle to the mold

 Equiaxed

zone

Within the liquid at the center there are generally many small equiaxed grains suspended throughout

As freezing continues, these small grains begin crowd together and finally block the inward motion of columnar grains

Metallic solid solution

most metal are combined to form alloy in order to impart specific characteristic The addition of impurity atoms to a metal will result in the formation of a solid solution A solid solution is a solid-state solution of one or more solutes in a solvent.

Such a mixture is considered a solution rather than a compound when the crystal structure of the solvent remains unchanged by addition of the solutes, and when the mixture remains in a single homogeneous phase.

Two terms in solid solution

Solute

Used to denote an element/compound present in a minor concentration

Element / compound that is present in the greatest amount a.k.a host atoms Characteristic of solid solution

Solvent

1. Form when solute atoms are added to the host material. 2. Crystal structure is maintained 3. No new structure formed 4. Compositionally homogeneous

Types of solid solution

( based from impurity point defects)

Substitutional Interstitial 1. Substitutional Host atoms are replaced/ substitute with solute/ impurity atoms. Factors to consider in substitutional s.s

Atomic size factors The difference in atomic radii between two atom is less than about 15% Crystal structure same crystal structures

 Electronegativity-

similar e/negativity/ smaller diff. Valances- similar valance electron

e.g system Ag-Au system Cu-Ni system Cu-Zn
system Crystal structure Ag Au Valences Atomic radius, 1.44 1.44 1.28 1.25 1.28 1.38 e/negativity Type alloy solubility

Ag-Au

FCC 1 FCC 1

1.9 2.4 1.9 1.8 1.9 1.6

substitional

complete

Cu-Ni

Cu FCC 2 Ni 2 FCC Cu Zn FCC HCP 2 2

substitional

complete

Cu-Zn

substitional

Not complete

2.

Interstitial solid solution

Impurity atoms fill the voids in the solvent atom lattice It interstices among the host atoms Atomic diameter of an interstitial impurity must be smaller than host atoms Normal max. allowable concentration of interstitial impurity atom is low (<10%)

Solution when 2 components combine to form a single phase Solubility Degree to which the two components mix Solubility limit The max. concentration of solute that may be added w/o forming a new phase

 Phase

A homogeneous portion of a system that has uniform physical and chemical characteristic
single-phase system homogeneous system Systems composed of two /more phases mixture/heterogeneous system

AluminumCopper Alloy

Phase diagrams

A graphical representation of the relationship between environmental constraints (e.g temperature and sometimes pressure), composition and regions of phase stability, ordinarily under condition equilibrium Example of Phase D. (binary)

3 types of Phase D.
Unary Binary Ternary

Binary Phase D.

Consists two elements or components in an alloy.

3 types of binary Phase D.

Complete solid solution No solid solution Limited solid solution e.g.

Cu and Ni are completely soluble Zinc has limited solubility in copper Sn has limited solubility in Pb Pb insoluble in copper

Binary isomorphous system (complete Solid solution)

Phase Diagram for Cu-Ni system

Isomorphous coz; Complete liquid & solid solubility Only one solid phase forms Same crystal structure. 3 diff. phase fields/ regions Liquid phase homogeneous liq. Solution (Cu + Ni) Two phase + L phase substitutional s. solution (consists both Cu-Ni)

PHASE DIAGRAMS: # and types of phases

Rule 1: If we know T and Co, then we know: --the # and types of phases present.

Cu-Ni phase diagram

PHASE DIAGRAMS: composition of phases

Rule 2: If we know T and Co, then we know: --the composition of each phase. Determination of phase compositions 1. located the temperature 2. if one phase present, the composition = overall composition (Co) of alloy 3. if two phase present, use tie line

PHASE DIAGRAMS: weight fractions of phases / relative amount phase

Rule 3: If we know T and Co, then we know: --the amount of each phase (given in wt%).

S WL R S R W R S

43 35 73wt % 43 32

= 27wt%

Binary eutectic for limited solids solution / partially solid solution

Characteristic: Solid are partly soluble in one another rather than be either completely soluble or completely insoluble
hypoeutectic hypereutectic Liq. Solution (L) a b

, = solid solution
ae, be = liquidus

L+
c e

L + +

ac, cd, bd = solidus

g B

cf, dg = solvus

Solvus cf denotes the solubility limit of B in A Solvus dg shows the solubility limit of A in B

Determination of phase and phase composition: Same as in Binary isomorphous system and eutectic no solid solution

Determination of weight fraction

hypoeutectic hypereutectic Liq. Solution (L) a R Q b Weight fraction of , W = R/(R+Q) Weight fraction of Liquid, WL= Q/(R+Q) g

L+

L +

+
B

Binary Eutectic Phase Diagram (1. No solid Solution)

Characteristic : system 2 components e. g A & B completely soluble in one another in liquid state but completely insoluble in one another
Temp
c f
L+ solid A L+ solid B

Liq. Solution (L)

Region above line ced=liq. Solution

Line ce and ed = liquidus Region below horizontal line feg = mixture of solid A & B Line cfegd= solidus .

e
solid A + solid B

Point e = eutectic point the lowest temp. at which a liq. solution can exist. Determination of phase and phase composition: Same as in Binary isomorphous system and eutectic limited solid solution Determination of weight fraction of phase
Liq. Solution (L) c P
L+ solid B

Weight fraction of solid A, WA = Q/(R+Q)

Weight fraction of Liquid,

WL= R/(R+Q)

solid A + solid B

Gibbs Phase rule

express the r/ship between no. of phases present and the no of externally controllable variables

Applies only at equilibrium system

P+f=c+n

P = no of phase present f = no. of degrees of freedom (state variables : temp, pressure & composition) c = no. of components n= no. of noncompositional variables

For condensate system

P+f=c+2

For alloy/ ceramic system P+f=c+1

Pressure s
B C

Ex: point A Phase : 1 Component : 1

F=2

A
Temp

how about point B and C? Binary system?

Cooling curves & phase diagram

different composition will give diff. cooling curves For pure metal., the cooling curves show horizontal thermal arrest at their freezes points The slope changes at L1-S1 etc, are corespond to the liquidus and solidus.
Freezing zone
L1 S1

L1 S1

Cooling curves for eutectic binary diagram

a)

b)

Cooling curve at eutectic alloy Cooling curve at hypo/hypereutectic alloy

B

alloy transformation at invariant equilibrium

Invariant equilibrium involve:
1. 2. 3.

3 phases co-exist in Exist only at one temperature / fixed temp. Composition for 3 phases co-exist is fixed at the point.

Common example of invariant equilibrium. 1. eutectic 2. Eutectoid 3. Peritectic 4. monotectic

Eutectic transformation l (liq.)

(s.s)

(s.s)

System- Ag-Cu, Pb-Sn

Eutectiod transformation +

(s.s)

(s.s)

(s.s)

System Fe-C, Al-C

Peritectic reaction transformation l

(Liq.)

+
(s.s)

(s.s)

System: Cu-Zn

Peritectiod reaction transformation

(s.s)

+
(s.s)

(s.s)

System: Al-Ni, Cu-Zn

Metatectic transformation (s.s)

l + (liq) (s.s)

System U-Mn

Monotectic transformation l1 (liq.) (s.s) l2 (liq)

System Cu-Pb

Syntectic reaction l1 + l 2
(liq.) (liq)

(s.s)

System: K-Zn, NaZn

Chapter 3 Iron-iron carbide phase diagram

Microstructure/microconstituent
Cementite (Fe3C) Form 1. Below 727oC, when solubility limit of carbon in ferrite is exceeded 2. Between 1147oC and 727oC when solubility limit of carbon in is exceeded

Crystal structure: orthorhombic Characteristics: hard and brittle, tensile strength , compressive strength

Metastable phase- remain as a compound at Tr

if Fe3C If Fe3C + C ( T) + C ( 650 -700oC for several year

The addition of third element e.g Si, Co, Al promotes graphitization Fe3C has a greater solubility in and than has graphite

Reaction : L

+ Fe3C + Fe3C

Austenite ( phase of iron)

Unstable below 727oC Maximum solubility of carbon in austenite, 2.14wt% at 1147oC Carbon solubility higher than in ferrite FCC structure FCC structure interstitial position larger than BCC. Interstitial larger , lower strains imposed on surrounding iron atoms , higher carbon solubility

Nonmagnetic Properties: highest tensile strength, moderate elongation and hardness properties.

Ferrite, iron

crystal structure: BCC Stable at room temperature

has magnetic properties

At above 768oC, the ferromagnetic properties disappear. Nonmagnetic props at 768oC to 912oC tensile strength , elongation , hardness , toughness low

 ferrite virtually = as ferrite except, stable at relatively high T. T range between 1394oC until Tm for pure iron Lower solubility of carbon in iron

Pearlite ( + Fe3C)

two-phase microstructure from transformation of austenite of eutectoid composition of alternating layer (lamellae) intermediate mechanical properties between & Fe3C

Resulted

Consists

PEARLITE MORPHOLOGY
Two cases:
Ttransf just below TE
--Larger T: diffusion is faster --Pearlite is coarser.

Ttransf well below TE

--Smaller T: diffusion is slower --Pearlite is finer.

- Smaller T: colonies are larger

- Larger T: colonies are smaller

8

observation under microscope: a white matrix is phase

Microstructure change

occurs either in cooling or heating process factors that influence the microstructure formation : crystal structure, physical & chemical properties, composition, processing (cooling rate, heat treatment)

Slow cooling of plain carbon steel

1.

At eutectoid plain carbon steel

Explanation microstructure changes at eutectoid

1.

2.

3.

At temperature _____ m/structure of is exist Further cooling process to the 727oC at eutectoid temperature or just below the Te, it will form a pearlite m/structure only pearlite for at composition eutectoid.

Additional information of pearlite at eutectoid.

At eutectoid , the relative layer thickness for and Fe3C ( 8:1)

Often termed colonies ( coz they form colony layers that oriented in essentially the same direction) Dif. colony dif. oriented direction

2. Microstructure changes at hypoeutectiod

Explanation
1.

At ____ , point __, the microstructure will consist entirely of grains of phases.

2.

In cooling to point___, at temp __, which is within + phase region, small will form along the original grain boundaries. (composition changes)
At point ___, just above the eutectoid, particles will have grown larger. (composition) As temp. lower, just below the eutectoid to point____, all phase that was present at temperature Te will transform to pearlite Below Te, m/structure phase present as a continuous matrix phase surrounding the isolated pearlite colonies

3.

4.

5.

6.

Ferrite present in pearlite (eutectoid ferrite) and proeutectoid (pre/before eutectoid) ferrite.

3. Microstructure changes at hypereutectiod

Microstructure changes (an explanation)

1.

At point ___& temp___, only phase will be present with a composition of C1

Further cooling to point ___, at + Fe3C region, the cementite phase will begin to form along the initial grain boundaries and called as proeutectoid cementite. As temperature is lowered through the eutectoid to point ____, all remaining austenite of eutectoid composition is converted to perlite

2.

3.