Classification of Materials

Most materials can be broadly classified into three main groups: metals ceramics and polymers. In addition, modern engineering materials include composites, semiconductors, and biomaterials.

Metals
-- normally combinations of metallic elements (alloys), e.g. Cu/Zn and Pb/Sn. -- optically opaque -- strong and ductile -- good electrical and thermal conductors -- mainly structural applications applications.

Ceramics
-- compounds of metallic and non-metallic elements, e.g. oxides and carbides bid -- can be optically transparent -- hard and brittle -- heat and corrosion resistant -- structural and functional applications
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Polymers
-- organic compounds of carbon, hydrogen and other non-metallic g p , y g elements, e.g. polyethylene and polystyrene -- low density, flexible and formable -- resistant to chemical attack -- mainly structural applications

Composites
-- composed of more than one material type, e.g. glass fiber in a polymer

matrix. ti -- combines best characteristics of each of the component materials -- high specific strength and fracture resistant -- mainly structural applications y pp

Semiconductors
-- electrical properties intermediate between conductors and insulators -- properties extremely sensitive to minute traces of impurity elements, e.g. ti t l iti t i t t fi it l t P and B in Si -- vapor processing of thin planar arrays of doped-Si forms the basis of the integrated circuit industry -- f functional applications ti l li ti
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Biomaterials Bi t i l
-- materials that are non-toxic when implanted in the human body -- used for replacement of diseased or damaged body parts, e.g. hip implants

Current Materials Challenges

-- reduce energy use in transportation systems by developing (1) low d i t t ti t b d l i l cost, high performance structural composites for weight reduction, and (2) ceramic engines for increased operating efficiency. -- develop materials for sustainable energy production systems, such systems as wind turbines and solar cells. -- improve quality of the environment by (1) developing cleaner materials refining and processing technologies, and (2) increasing recycling efforts. -- develop nanostructured materials and technologies for the next generation of miniaturized engineered systems.

Atomic Bonding in Solids

A. Primary Bonds
Strong bonds (~100 kcal/mol) arising from transfer or sharing of valence electrons. 1. Ionic bond -- transfer of valence electrons -- electron localization (ionic species) -- non-directional bonding -- NaCl, ZnO, Li2O, etc. -- extremities of Periodic Table t iti f P i di T bl 2. Covalent bond -- sharing of valence electrons -- partial electron delocalization (molecular unit) -- hybridization of electron orbitals -- highly directional bonding -- H2, H2O, CH4, graphite, diamond, fullerene, etc.
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3. Metallic bond -- complete sharing of valence electrons (free electron gas) -- complete electron delocalization l t l t d l li ti -- non-directional bonding -- no valency restrictions (alloying) -- Fe, Cu, Fe-Ni, Cu-Zn, etc.

B. Secondary Bonds
Weak bonds (~1 kcal/mol) arising from dipole interactions. Responsible for bonding between electrically neutral atoms or molecules 1. Permanent dipole p g g -- arises when centers of positive and negative charge in a molecule do not coincide -- directional -- asymmetric polar molecules, such as H2O, H2S, NH3, CF2H2, etc. 2. Induced dipole -- arises from permanent dipole in one molecular group inducing a dipole in a neighboring group -- di directional ti l
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3. Fluctuating dipole -- arises from fluctuating charge distribution (no permanent dipole) -- non-directional -- inert gases (Ne, Ar ) and symmetric molecules (CH4, CCl4, ) (Ne Ar, ) )

C. Hydrogen Bond
Intermediate bond (~5 kcal/mol) -- arises when H atom forms a bridge between two electronegative atoms -- highly directional y , , -- nylon, cellulose, etc.

D. Addition (or Chain) Polymerization

Polymerization consists of joining a large number of molecules together -- b k double bond gives two carbon orbitals for bonding broken d bl b d i t b bit l f b di -- directional -- chain-like structure that is called a polymer -- polyethylene, polystyrene, etc. p y y ,p y y ,

Schematics of Secondary Bonds

(a) Electrically symmetric atom (b) Induced atomic dipole

Hydrogen bonding in hydrogen fluoride (HF)

Polar hydrogen chloride (HCl) molecule

Ionic Bond o c o d
This is easiest to visualize: -- results from strong electrostatic attraction between oppositely charged ions -- stable ionic aggregates due to ions with filled outer shells -- non-directional bonding permits close packing -- combination of elements with low ionization energy (e.g. Na) and high electron affinity (e.g. Cl)

Ionization Energy is the energy required to remove the least tightly bound electron from an atom (forms positive ion) Electron affinity is the energy released when an electron is captured by an atom (forms negative ion).

Figure 1 An example of an ionic bond showing electron transfer from Na to Cl to form N + cation and Cl- anion pair. f N t t f Na ti d i i The ionization energy of Na Na+ is 5.14 eV, whereas the electron affinity of Cl Cl- is 4.02 eV. Hence, the net energy (work) required y , gy ( ) q to create a pair of isolated Na+ and Cl- ions is 1.12 eV.
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Figure 2 (a) The bond force curve showing the location of the equilibrium bond-force separation distance x0. Note the approximately linear slope of the total force curve in the vicinity of x0. (b) The bond-energy curve for the ionic compound NaCl showing the location of the equilibrium separation distance x0. Interaction Energy Consider the interaction between two point charges Q1 and Q2 separated by distance r.
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The interaction energy E is the sum of two terms: attractive energy EA and repulsive energy ER E = EA + ER (attractive) (repulsive)

Q1Q2 4or

b rn

(1)

(negative) (positive) o is permittivity of vacuum, b and n are constants, which depend on ion type; n ~ 8-10.

dE dr

r = r*

=0

QQ dE nb = 1 22 (n+1) = 0 dr 40 r r
Rearranging terms

1 QQ b 1 2 =+ n n 40 r * (r*)

(2)
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Now from (1)

Q1Q2 b Eb = + 40 r * (r*)n
Substituting (2) in (3)

(3)

Eb =

Q 1Q 2 1 1 4 0 r * n

Cohesive Energy gy

Figure 3A unit cell for the rock salt, or sodium chloride (NaCl) crystal structure.

Na+ ion has 6 first nearest neighbor Cl- ions at r*. Na+ ion has 12 second nearest neighbor Na+ ions at 2 r*. etc. By summing the contributions from all ions, it can be shown that the cohesive energy/mol is h i / li

N Q1Q 2 A 1 E= 1 4 0 r * n
where N is Avogadros number, and A is the Madelung constant, which depends on structure type. For NaCl, one electronic charge is involved in transfer of valence electron; hence Q1 Q2 = (+e) (-e) = -e2

Ne 2 A 1 E= 1 4 0 r * n
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Substance Na N +ClZn++O--

A 1.75 1 75 1.64

r*() 2.81 2 81 1.97

n 8 8

Cohesive energy (kcal/mol) 181 964

Shorter bond distance r for ZnO reflects stronger interaction energy between r* divalent ions. Since Q1Q2 = (-2e) (+2e) = - 4e2 for ZnO, the cohesive energy/mol is at least four times that of NaCl. ti th t f N Cl

Characteristics of Ionic Crystals

Coordination number is defined as number of nearest neighbors at the bond distance. distance -- NaCl has CN = 6 -- other ionic crystals have different values, e.g. CsCl has CN = 8 -- determined by relative size of anion and cation
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Ionic Radius is defined as the radius of the hard sphere that represents the ion. -- radius of anion is usually larger than that of the neutral atom. -- radius of cation is usually smaller than that of the neutral y atom. Element Charge at given radius +1 -1 1 +2 -2 Ionic radius () 0.98 1.81 1 81 0.78 1.32 Atomic radius () 1.86 0.91 0 91 1.59 0.60

Sodium Chlorine Chl i Magnesium Oxygen

CN = 6
Consider NaCl structure (see Table 1), where each Na+ cation is surrounded by six Cl- anions at the bond distance. distance
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RA = ionic radius of anion (Cl-) RC = ionic radius of cation (Na+)

[2(R A + R C )]2 = (2R A )2 + (2R A )2

2(RA + RC) = 8 RA = 2 2 RA

RC = 2 1 RA
RC = RA

2 1 = 0.414
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This is the smallest value of RC/RA for which all 6 anions touch the cation, called the critical radius ratio. -- larger values allowed -- smaller values not allowed

Figure 4 Stable and unstable anion-cation coordination configurations; large circles represent anions; small circles represent cations.

CN = 4
Consider ZnS structure (see Table 1), where each Zn2+ cation (0.83) is surrounded by four S2- anions (1.74) at the bond distance.

2R A = 2

RA + RC =

3 2
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Table 1. The critical (r/R) ratio for each coordination number.

RC =

3 2 2

RC 6 = 1 = 0.225 0 5 RA 2

Note that for crystals having equal numbers of anions and cations only CN values cations, of 2, 3, 4, 6, 8 and 12 satisfy symmetry requirements.

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Crystal Structures
We have examined the forces responsible for aggregation of atoms or molecules. Now we will consider how they are organized or distributed in space. Periodic arrays crystalline materials Random arrays amorphous materials Combination arrays semicrystalline materials

Crystal lattice is defined as an array of points, infinite in extent, in which every point has identical surroundings. i t h id ti l di Unit cell is the smallest region that completely defines the crystal lattice g p y y -- vertices of unit cell are known as lattice points -- lengths of unit cell are known as lattice parameters

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Figure 5 Possible unit cells for a 2-D space lattice: (a) square, (b) rectangle, and (c) parallelogram. There are 14 possible arrangements for 3-D lattices, which are known as Bravais lattices. These can be grouped into 7 crystal systems, based on edge lengths of unit cell (unit vectors) and the angles between them.
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Figure 6 The 14 Bravais lattices grouped into the 7 crystal systems. The restrictions on the lattice parameters a, b, and c and the angles between the edges of the unit cell , , and are listed for each unit cell.

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Miller Indices
Most M t common convention used t d ti d to denote points, directions, and planes t i t di ti d l in crystal lattices

Points
Right-hand Cartesian coordinate system used to denote specific points, e.g. 1,0,0.

Directions
Specific directions denoted by square brackets, e.g. [111]. Families of directions denoted by angle brackets, e.g. <111>
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Angle between directions [h1k1l1] and [h2k2l2] is given by:

cos =

(h1h 2 + k1k 2 + l1l 2 ) (h12 + k12 + l12 ) (h 22 + k 22 + l 22 )

Planes
Defined as the reciprocals of the intercepts on coordinate axes

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Specific planes denoted by parenthesis, e g (111) parenthesis, e.g. (111). Families of planes denoted by braces, e.g. {111}. braces,
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Structures of Metals
Three main types:
-- body centered cubic (bcc) -- face centered cubic (fcc) -- hexagonal close packed (hcp) g p ( p)

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fcc d h f and hcp structures formed by different stacking sequences of close-packed t t f d b diff t t ki f l k d planes. ABABABA.hcp Both have ABCABCA.fcc ABCABCA fcc CN = 12

Figure 7 Close packed stacking sequence (ABCABCA) for fcc structure

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Figure 8 Close packed stacking sequence (ABABABA) for p hcp structure.

Density
Calculate the density of fcc aluminum: atomic mass = 26.98; a = 4.04 x 10-8 cm; A0 = 6.02 x 1023 mol-1

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m 17 .93 x 10 23 = = = 2 .72 g / cm 3 v 65 .94 x 10 24

Actual A t l measured d d density is 2.70 g/cm3 it i 2 70 /

Packing Factor
Calculate packing factor (PF) for bcc, fcc and hcp structures. (PF = volume of atoms/volume of unit cell)

bcc structure

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PFbcc

(43 r ) =2
3 3 a0

4r Since ao = 3

PFbcc =

3 = 0 68 0.68 8

fcc structure

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PFfcc

(4 3 r 3 ) =4
a3 0

Since a0 =

4r 2
3 2 = 0.74

PF fcc

hcp structure p
Same as for fcc, since both structures are ideally close-packed, with CN = 12. PF hcp = 0.74
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Interstitial Sites
The locations of the largest holes in bcc, fcc and hcp structures are known as interstitial sites

fcc structure
Largest hole in an fcc structure is located at the center of the unit cell. -- known as an octahedral site, since the polyhedron connecting nearest neighbor atoms has 8 sides -- there are 12 equivalent octahedral sites located at edge centers of the unit cell -- each edge site is shared by four unit cells, hence there are 4 = [(12 x ) + (1 x 1)] octahedral sites per unit cell -- if hole radius is k, then the radius ratio k/r = 0.414 -- hence, atoms about 40% of the size of the host atoms can fit into octahedral sites The fcc structure also contains tetrahedral sites, located at , , -type positions in the unit cell. -- there are 8 equivalent tetrahedral sites that lie completely within the unit cell
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-- the radius ratio, k/r, for a tetrahedral site is 0.225 -- hence atoms about 20% of the size of the host atoms can fit into hence, tetrahedral sites Thus, there are twice as many tetrahedral sites as octahedral sites, and each t t h d l site i about one-half th di h tetrahedral it is b t h lf the diameter of an octahedral site. t f t h d l it

bcc structure
This structure also contains both octahedral and tetrahedral sites -- octahedral sites are located at face centers and edge centers of the unit cell, giving a total of 6 sites per unit cell and k/r = 0.155. -- t t h d l sites are l tetrahedral it located at 0 t t d t , , type positions, giving a iti i i total of 12 tetrahedral sites per unit cell and k/r = 0.291. Thus, there are twice as many tetrahedral sites as octahedral sites, and each tetrahedral site is about twice the diameter of an octahedral site.

hcp structure
Similar to fcc, as indicated in Table 2.
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Table 2. The size and number of tetrahedral and octahedral interstitial sites in the BCC, FCC, and HCP crystal structures. The sizes of the interstitial sties are given in terms of the radius ratio (k/r) where k is the radius of the largest atom that can fit into the interstitial position and r is the radius of the host atoms. The number of interstitial sites is given in terms of both the number of sites per cell and, in parentheses, the number of sites per host atom.
Crystal Structure Size of tetrahedral sites / k/r = 0.291 k/r = 0.225 k/r = 0.225 Size of octahedral sites k/r = 0.155 / k/r = 0.414 k/r = 0.414 Number of tetrahedral sites per unit cell (per host atom) 12 ( ) (6) 8 (2) 12 (2) Number of octahedral sites per unit cell (per host atom) (3) 6( ) 4 (1) 6 (1)

BCC CC FCC HCP

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Figure 9 The locations of the interstitial sites in the common crystal structures: (a) octahedral sites in FCC, (b) tetrahedral sites in FCC, (c) octahedral sites in BCC, (d) tetrahedral sites in BCC, (e) octahedral sites in HCP, and (f) tetrahedral sites in HCP.
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Structures of Ceramics
The structures of many ceramic crystals can be visualized in terms of y y stacking of close-packed planes of anions, with interstitial sites occupied by the cations. Two types of interstitial sites: -- tetrahedral (CN=4) -- octahedral (CN=6) Crystal structures determined by: -- stacking sequence (fcc vs. hcp) g ( ) -- manner in which interstitial sites are occupied Figure 10 -- The stacking of one p plane of close-packed spheres p p (anions) on top of another: tetrahedral and octahedral positions between the planes are designated by T and O, O
respectively

Example NaCl structure close-packed -- fcc array of close packed anions of the {111} type -- cations reside in octahedral sites, each with 6 nearest neighbor anions -- all octahedral sites are occupied
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Density

Figure 11 A section of the rock salt crystal structure from which a corner has been removed. The exposed plane of anions (dark spheres inside the triangle) is a {111}-type plane: the cations (light spheres) occupy the interstitial octahedral positions.

*Other ionic structures can be understood in similar manner.

Density

n( A c + A A ) = Vc N A
n = number of formula units within unit cell Ac = sum of at. wt. of cations AA = sum of at. wt. of anions Vc = volume of unit cell NA = Av. number

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Calculate the density of NaCl.

n =4 AC = ANa = 22 99 g/mole 22.99 AA = ACl = 35.45 g/mole VC = a3

a = 2 rNa + + 2 rCl

Vc = a 3 = 2 rNa + + 2 rCl 3

r Na
rCl

= 1 02 1.02
= 1 . 81

[2(1.02 10

4(22.99 + 35.45)
8

+ 1.81 10

8 3

)] 6.023 1023
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= 2 . 14 g . / cm 3
The experimental value is 2.16 g/cm3

AX-Type Crystal Structures

Equal numbers of cations and anions, known as AX compounds.

NaCl
(CN = 6)

ZnS
(CN = 4)

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39

AmXP-Type Crystal Structures

When charges on cations and anions are not the same, a compound with the formula AmXP can exist, e.g. CaF2

RC/RA = 0.8, so that CN = 8 half of center positions only are occupied by Ca2+ ions

AmBnXP-Type Crystal Structures yp y

Compounds that have more than one type of cation (A and B) formula for barium titanate is B)formula BaTiO3 (perovskite structure).
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Silicate Ceramics
The basic building block of all silicate ceramics (amorphous and crystalline) is the tetrahedron. y yg -- each silicon atom is tetrahedrally bonded to four oxygen atoms -- since each oxygen atom requires an extra electron to achieve a stable electronic structure, a charge of 4 is associated with every tetrahedron.

Figure 12 A silicon-oxygen (SiO4) 4- tetrahedron. Si4+ = 0.39 O2- = 1.32 Hence r Si (ion) /r O (ion) = 0.3
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This value is within the stability range 0.225 r/R < 0.414 (Table 3) for tetrahedral coordination (CN=4). Since the Si-O bond is mixed ionic and covalent (about 50:50), the tetrahedron satisfies the bonding ( ), g requirements of both ionic radius ratio and covalent directionality. Various silicate ceramics arise from the different ways in which the (Si04)4- units combine into one two or three dimensional structures one-, two-, three-dimensional structures. Because of the high charge on the Si4+ ion, the tetrahedral units are seldom joined edge to edge and never face to face, but almost always share corners, with no more than two tetrahedra sharing a corner.

Figure 13 Effect of corner edge, and face sharing on cation-cation separation. Th distances S1:S2:S3 are i the ratio 1:0.58:0.33; th t i ti The di t S S in th ti 1 0 58 0 33 that is, cation-cation repulsion increases on going from left to right, which tends to destabilize the structure.

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43

Silica
Silicon dioxide or silica (SiO2) has a three-dimensional structure, such that three dimensional every corner oxygen atom in each tetrahedron is shared by adjacent tetrahedra. y y -- most common crystalline forms are quartz, cristobalite and tridymite. -- relatively open structures of low density -- high melting points, due to strength of Si-O bonds

Figure 14 2-D representations of (a) silica glass, (b) crystalline silica.

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Silica glass
Also known as vitreous silica, silica glass has a highly disordered structure, i.e. it lacks the long-range order characteristic of crystalline silica, Fig. 14.

-- Oxides, such as B2O3 and GeO2, which readily form glassy structures, are referred as network formers. When added to a formers. silica glass, they substitute for the silicate t t h d , so th t the ili l th b tit t f th ili t tetrahedra tetrahedra, that th longlong-range order is retained.
45

-- Oxides, such as Na2O and K2O, which are incapable of forming glassy structures, are referred as network modifiers. When added to a silica glass, they break-up the tetrahedral network and create a more disordered structure. -- O ides such as TiO2 and Al2O3, in which the cations substitute for Oxides, s ch hich s bstit te silicon and help to stabilize the network, are called intermediates. The addition of modifiers and intermediates lowers the melting point and viscosity of the glass, making it easier to form into useful shapes. Thus, glass containers and windows are made from low melting point soda-limesilica glasses, while furnace tubes are made from high melting point vitreous silica. Pyrex, a glass composition containing the network formers SiO2 and B2O3, and the network modifiers Na2O and CaO, has properties intermediate d th t k difi N dC O h ti i t di t between those of soda-lime-silicate glass and vitreous silica, e.g. it has about three times the thermal shock resistance of silica glass, but does not require g p g p the high processing temperature of vitreous silica.

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Layered silicates
A two dimensional sheet is formed by sharing of three oxygen atoms in two-dimensional a planar array of tetrahedra. -- formula unit is (Si2O5)2-- a negative charge is associated with the unbonded oxygen atoms projecting out of the plane.

Figure 15 Schematic representation of the twotwodimensional silicate sheet structure having a repeat unit formula of (Si2O5)2-.

Such a negatively charged sheet can bond with an equivalent positively charged sheet to form an electrically neutral structure. -- sheet or layered silicate structures are characteristic of clays and other minerals 47

-- bonding within a two-layered sheet is strong (ionic-covalent), whereas bonding between adjacent sheets is relatively weak (van der Waals).

Clays
Aluminosilicates that contain chemically bound water. -- crystal structures are relatively complicated -- when water is added, clays become very plastic; so-called added hydroplasticity -- can be fired at relatively low temperature to form a dense and strong ceramic

Kaolinite
Compound is formed by bonding between Al2(OH)42+ and (Si2O5)2- layers. -- formula unit is Al2(OH)4 Si2O5 -- crystalline kaolinite is composed of many such double layers, stacked one upon the other -- additive to paper products
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Figure 16 The structure of kaolinite clay.

Talc
Compound comprises 1 sheet of Mg3(OH)24+ + 2 sheets of (Si2O5)2-- formula unit is Mg3(OH)2 (Si2O5)2 -- slips easily, like graphite -- absorbs water
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Glass Properties
Glass transition temperature
For an amorphous or non-crystalline material, the glass transition temperature (Tg) is the critical temperature that separates glassy p ( g) p p g y behavior from rubbery behavior, in the time scale of the experiment. -- most easily detected via measurements of changes in y g specific volume (1/ = v/unit mass) associated with heating or cooling a material -- upon heating, the material undergoes a transition from the glassy state to the supercooled liquid state, and then to the fully liquid state.

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Figure 17 Specific volume as a function of temperature for a series of materials. materials (a) The liquid-to-crystalline solid transformation. A transformation discontinuous change in volume occurs at the melting temperature Tm. (b) The liquid-to-glass transformation (the liquid-to-crystal curve is shown for reference). The temperature range in which the slope of the liquid-glass curve changes is the glass transition temperature Tg. (c) Specific volume versus temperature for a semicrystalline material. The discontinuous 51 change in volume occurs at Tm, and a change in slope occurs at Tg.

Viscosity-temperature behavior y p
The temperature dependence of the viscosity of a glassy material is the key to proper selection of processing parameters. -- melting point (viscosity 100 P) is the temperature where the glass is fluid enough to be considered a liquid. -- working point (viscosity 104 P) is the temperature where the glass is easily deformed. -- softening point (viscosity 4 x 107 P) is the maximum temperature where glass can be handled without distortion. h l b h dl d ith t di t ti -- annealing point (viscosity 1013 P) is the temperature were any residual stress in the glass can be eliminated. -- strain point (viscosity 3 x 1014 P) is the temperature where fracture occurs before plastic deformation. Most glass-forming operations are carried out in the working range, which is between the working and softening temperature.
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Figure 18 Logarithm of viscosity versus temperature for fused silica and several silica glasses.

53

Structures of Polymers
Hydrocarbon molecules
Most polymers are derived from hydrocarbon precursors. It is instructive, therefore, to consider the structures of some typical hydrocarbon , yp y molecules. All four valence electrons in carbon participate in bonding. Moreover, hybridization of s and p orbitals of the valence electrons gives directional bonding. -- 4 equivalent sp3 orbitals, as in methane and ethane -- 3 equivalent sp2 orbitals, as in ethylene -- 2 equivalent sp1 orbitals, as in acetylene

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single bond

-- formed by overlapping sp3 orbitals with the orbitals of other atoms double bond -- formed by overlapping sp2 orbitals with the orbitals of two different carbon atoms triple bond -- formed by overlapping sp1 orbitals with the orbitals of two different carbon atoms

Saturated hydrocarbons

sp3 orbitals of both CH4 and C2H6 directed towards the corners of a regular tetrahedron

55

Unsaturated hydrocarbons

56

Polymer molecules
Directional nature of covalent bonds enables carbon atoms to form long-chain molecules. -- Activator (catalyst) is needed to start p ( y ) process of p y polymerization. For example, ethylene gas can be transformed into polyethylene solid by heating under pressure in the presence of a catalyst. -- Polymerization process begins when an active mer is formed by reaction of an ethylene gas molecule with a catalyst species (R). ti f th l l l ith t l t i (R ) Polymer chain is then formed by the sequential addition of polyethylene monomer units. In so doing, the active site is transferred to each end-unit monomer as it is linked to the growing chain.

57

Activator (catalyst) is needed to start process of polymerization. For example, ethylene gas can be transformed into polyethylene solid by heating under pressure in the presence of a catalyst. The polymerization process begins when an active mer is formed by reaction of an ethylene gas molecule with a catalyst species (R). The polymer chain is then formed by the sequential addition of polyethylene monomer units. In so doing, the active site is transferred to each endunit monomer as it is linked to the growing chain. chain

The final result, after successive additions of ethylene monomer units result units, is a long chain polyethylene molecule. Carbon atoms form a zig-zag backbone in the molecule, with an angle of 109 between the bonds; the C-C bond length is 0.154 nm.

58

Figure 19 For polyethylene, (a) a schematic representation of mer and chain structures, and (b) a perspective of the molecule, indicating the zigzag backbone structure. Hence, the formula unit for a polyethylene molecule may be represented as follows, where n is the number of ethylene molecules t d f ll h i th b f th l l l (monomers) that bond together to form the long chain molecule.
H | C | H C | H n H
|

59

Mer structures for some common polymeric materials ate a s

60

The molecular structures of PTFE, PVC and PP are shown in Figure 21. In PTFE, all the hydrogen atoms in polyethylene have been replaced by fluorine atoms, whereas in PVC and PP every fourth hydrogen atom along the chain has been replaced by Cl or CH3 (methyl group).

Figure 20 Mer and chain structures for (a) l t t fl ( ) polytetra-fluoroethylene, (b) polyvinyl th l l i l chloride, and (c) polypropylene.

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Molecular shape
Long chain molecules are capable of rotation and b di L h i l l bl f i d bending i three in h dimensions. This is because any carbon atom in a chain can lie at any point on the cone of revolution (109 angle) with the bond of the preceding carbon atom, Figure 22. Thus, a long chain molecule typically has a very complex shape, involving many bends, twists and kinks.

Figure 21 Schematic representations of how polymer chain shape is influenced by the positioning of backbone carbon atoms (solid circles). For (a), the rightmost atom may lie anywhere on the dashed circle and still subtend a 109 angle with the bond between the other two atoms. Straight and twisted chain segments are shown in (b) and (c), respectively.

62

Polymer crystallinity
The crystalline state of a polymer is more complex than that of a metal or ceramic, because of the difficulty of aligning the long chain molecules in a regular close-packed structure. However, it does occur readily in molecules, such as PE and PTFE, where the atoms are arranged symmetrically along the carbon backbone. Polyethylene can be t i ll l th b b kb P l th l b crystallized with the orthorhombic structure, Figure 23, which represents the closest packing of the long chain molecules.

Figure 22 Arrangement of molecular chains in a unit cell for polyethylene polyethylene.

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-- degree of crystallinity may range from completely amorphous up to about 95% crystalline -- density of a crystalline polymer is greater than its amorphous counterpart because of the closer packing of molecules in the crystalline state -- degree of crystallinity achieved by a polymer depends on the cooling rate f t from th li id state the liquid t t -- many bulk polymers that are crystallized from the melt form spherulites, Fig. 24, which are considered to be the polymer equivalents of grains in polycrystalline metals and ceramics,

Figure 23 A transmission photoFi i i h micrograph (using cross-polarized light) showing the spherulite structure of polyethylene. Linear boundaries form between adjacent spherulites, and within each spherulite appears a Maltese cross. 525 .
64

Polymer characteristics
1. Side groups
-- clusters of atoms that are attached to the carbon backbone

2. Degree of polymerization
-- defines average chain size of a polymer

3. Cross linking
-- joining of two chains together by an atom, group of atoms or another chain 4. Elastomers -- polyisoprene experiences large elongations under load, and returns to its original shape upon unloading -- trans-poly on opposite sides (rigid solid) -- cis-poly on same side (steric hindrance) causes kinking, i.e. chains to cis poly coil.
65

5.Vulcanization
-- cross-linking process in elastomers; non-reversible reaction at elevated temperatures using sulfur compounds -- automobile tires have 3-5% S and are elastic -- battery cells have more S and are more rigid

6.Stereoisomerism
-- same composition but different structure isotactic all on one side syndiotactic alternating side groups atactic randomly on opposite sides

7.Thermoplastic polymer p p y
-- softens when heated and hardens when cooled (reversible process), as in polyethylene -- due to breaking and reforming of weak secondary bonds between chains

8.Thermosetting resin
-- decompose before they soften because of extensive cross linking, as p y g, in epoxy resin
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9. Conformation
-- this refers to the outline or shape of the long chain molecule -- can be modified by a simple bond rotation

10. Configuration
-- this refers to the arrangement of atoms positions along the chain -- can be altered only by breaking and reforming primary bonds

Melting and crystallization

Carbon backbone of a long chain polymer is strong, since it is composed of a chain of C-C primary b d In the crystallized state, the close-packed h i fCC i bonds. I th t lli d t t th l k d segments of the long chain molecules are held together by weak secondary bonds It follows that when a crystalline polymer is heated, thermal energy can easily disrupt the regular periodicity of the crystalline domains, thereby forming a disordered network of long chain molecules. As in ceramics, melting and solidification occurs over a temperature range, T = Tm Tg. Fig. Fig 24 shows this effect for three different cooling rates from the fully molten state, leading to a glassy solid (fast), semi-crystalline solid (intermediate), and crystalline solid (slow)
67

Figure 24 Specific volume versus temperature, upon cooling from the liquid melt, for melt totally amorphous (curve A), semicrystalline (curve B), and crystalline (curve C) polymers

Polyethylene readily crystallizes by slow cooling from the melt, whereas polystyrene does not, due to the presence of bulky side groups (benzene rings) g ) -- abrupt changes in elastic stiffness, heat capacity and thermal expansion coefficient occur at Tg -- processing of thermoplastic polymers is carried out within the critical temperature range T = Tm Tg, where the material is in its softened, rubber-like state.
68

Structures of Carbon
Elemental carbon exists in three distinct polymorphic forms: El t l b i t i th di ti t l hi f -- diamond -- graphite -- fullerene

Diamond

Graphite

C60 Fullerene

Graphite
A stable form of carbon graphite consists of layers of strong covalently carbon, strong, covalentlybonded carbon atoms, with weak Van der Waals bonding between the layers. Hence, the properties of graphite are anisotropic. -- good solid lubricant, because of ease of interplanar cleavage g , p g -- high in-plane strength and good stability at high temperature -- high in-plane electrical and thermal conductivity
69

In addition, graphite has high resistance to thermal shock, high absorption of gases, and good machinability. Applications include heating elements, rocket nozzles, electrical contacts, battery electrodes, and air purification , , y , p devices.

Diamond
A metastable form of carbon, diamond is composed entirely of strong covalently-bonded carbon atoms, with tetrahedral coordination. The properties of diamond are exceptional in many respects. -- hardest known material -- very low electrical conductivity -- unusually high thermal conductivity -- optically transparent in the visible and infrared -- high index of refraction Synthetic diamonds are produced commercially by a high pressure-high temperature process. Industrial grade diamond grits are used for grinding and cutting operations, and polycrystalline diamond compacts are used for rock drill bits and machine tools. Thin films of diamond are also manufactured by a Chemical Vapor Deposition (CVD) process. Such films are used as wear resistant coatings process. on drills, bearings, dies, and lenses. lenses. 70

Fullerenes
Discovered in 1985, C60 fullerene is a molecular form of carbon that consists of a hollow spherical cluster of sixty carbon atoms. -- same symmetry as that of a soccer ball -- composed of 20 hexagons and 12 pentagons, such that no two pentagons share a common side -- named after Buckminster Fuller inventor of the geodisic dome; Fuller, each C60 molecule is a molecular analogue of such a dome. -- other molecular forms with larger numbers of carbon atoms have been found -- properties of these fullerene molecules are being investigated Recently, methods have been found to produce nanoscale tubular and polyhedral structures. C b l h d l t t Carbon nanotubes di l very high specific t b display hi h ifi strengths. Many structural applications for this new class of superstrong carbon fibers are envisioned envisioned.
71

72

Polymer characteristics
1. 1 Side groups
-- clusters of atoms that are attached to the carbon backbone

2. Degree of polymerization
-- defines average chain size of a polymer

3. Cross linking
-- joining of two chains together by an atom, group of atoms or another chain 4. Elastomers -- polyisoprene experiences large elongations under load, and returns to its original shape upon unloading -- trans-poly on opposite sides (rigid solid) -- cis-poly on same side (steric hindrance) causes kinking, i.e. chains to coil.

5. Vulcanization
-- cross-linking process in elastomers; non-reversible reaction at elevated temperatures using sulfur compounds -- automobile tires have 3-5% S and are elastic -- battery cells have more S and are more rigid
1

Elastomers
Polyisoprene experiences large elongations under load, and returns to its original shape upon unloading g p p g

cis-poly on same side (steric hindrance) causes kinking, i.e. chains to coil (flexible solid)

trans-poly on opposite sides (rigid solid)

Vulcanization
Cross-linking Cross linking process in elastomers; non-reversible reaction at elevated non reversible temperatures using sulfur compounds

6.Stereoisomerism
-- same composition but different structure p isotactic all on one side syndiotactic alternating side groups atactic randomly on opposite sides

7.Thermoplastic polymer
-- softens when heated and hardens when cooled (reversible process), as in polyethylene -- due to breaking and reforming of weak secondary bonds between chains

8.Thermosetting resin
-- decompose before they soften because of extensive cross linking as linking, in epoxy resin

9. Conformation
-- this refers to the outline or shape of the long chain molecule -- can be modified by a simple bond rotation

10. Configuration
-- this refers to the arrangement of atoms positions along the chain -- can be altered only by breaking and reforming primary bonds
3

Stereoisomerism
Same composition but different atomic arrangement: S iti b t diff t t i t

Isotactic R groups all on one side

Syndiotactic R groups alternating on opposite sides

Atactic R groups randomly on opposite sides

Binary Phase Diagrams

Relevant terms
-- component is a pure element (e.g. Fe, Si, or B) or stoichiometric compound (e.g. NaCl, Al2O3, or Si3N4), i.e. a component is a chemically distinct substance. -- system is the volume occupied by a substance or series of alloys (e.g. Fe-C, Al2O3-Cr2O3, or ice-water). -- phase is a chemically and structurally homogeneous region of a material. -- homogeneous region is a region (or volume) in which the properties of a system are uniform. -- phase diagram is a map of the regions in which the different phases exist when the system is in equilibrium. -- solid solution describes the substitution of solute in solvent without a phase change.

Examples
-- pure fcc-Cu is a single component (Cu), single phase (fcc) system. -- a mixture of ice and water is a single component (H2O) system composed of two phases. -- a mixture of bcc-Fe (ferrite) and fcc-Fe (austenite) is a single component system composed of two phases. -- solid solution of Cu-Ni (or NiO-MgO) is a two-component, singlephase system.

One-component system
Simplified case, where phase relationships may be represented on a pressure-temperature diagram.

Fig. 25 - The equilibrium temperature-pressure diagram for iron.

Fig. 26 Pressure-temperature phase diagram for SiO2.

Phase equilibria can be described by the Gibbs phase rule F=CP+2 which relates number of degrees of freedom, F, at equilibrium to number of components, C, in the system, number of phases in equilibrium, P, and the two state variables temperature and pressure.

In a one-component system, such as Fe or SiO2 - if 3 phases are in equilibrium, then F = 1 3 + 2 = 0. This means that there is no freedom in specifying variables, so that the 3 phases can exist only at a point - triple point. -- if 2 phases are in equilibrium, then F = 1 2 + 2 = 1. This means that if one variable is changed (T) then the other is automatically fixed (P), so that the 2 phases can exist along a line - phase boundary line.

Two-component system
Most practical materials are composed of two components, and, since pressure is usually fixed at 1 atmosphere, the important variables are temperature and composition. In such cases, the appropriate expression for the phase rule is F=CP+1 When pressure is eliminated as a variable, a two-dimensional phase diagram can be constructed, showing the regions of composition and temperature where the different phases are in equilibrium.

Specifying composition
In many practical situations, compositions are specified as weight percentages (wt.%) or weight fractions of components. Alternatively, compositions may be specified in terms of atomic percentages (at.%) or atomic fractions.

wt.% A at.wt.A at.% A = 100 wt.% A wt.% B at.wt. A + at.wt. B

Similarly

at.% A at.wt.A wt.% A = 100 at.% A at.% B at.wt. A + at.wt. B

Example
Calculate the atomic percentage of C in Fe for a two-component alloy containing 0.8 wt.% C.

0.8 12 at.% C = 100 0.8 99.2 + 12 55.85

= 3.63 at.% C In ceramic systems, compositions are usually expressed as mole fractions. If mole fraction of component A is NA, then

NA =

nA (n A + n B )

where nA and nB are the numbers of moles of components A and B, respectively.

Isomorphous system
This is the simplest two-component phase diagram. -- displays complete solubility in both liquid and solid states over the entire composition range. -- for any mixture of the two components, solidification occurs over a temperature range, rather than at a specific temperature, as is the case for a pure component. -- liquidus curve separates single-phase liquid region from two-phase (solid + liquid) region. --solidus curve separates two-phase (solid + liquid) region from single-phase solid region.

Fig. 27 - An idealized binary (A-B) phase diagram with associated definitions.

Hume-Rothery rules
In order to form a substitutional solid solution over a wide range of compositions, the following conditions must be met: -- crystal structures of the two components (A and B) must be the same -- size difference between components must not differ by more than ~ 15%. -- valences of the two components must be similar -- electronegativities of the two components must be comparable These conditions are satisfied for many metallic and ceramic systems, e.g. Cu-Ni, Ag-Au, NiOMgO, Al2O3-Cr2O3. Fig. 28 Binary isomorphous systems Cu-Ni and NiO-MgO

Lever rule
The relative amounts of two phases in the semi-solid (solid + liquid) region can be determined by the lever rule. Amount of liquid of comp. CL = Amount of solid of comp. Cs =

(Cs Co ) p = (p + q ) ((Cs CL )
(C CL ) q = o (p + q ) ((Cs CL )

where Co is the composition of the mixture.

A CL C0 CS B

wt.% B

Cooling curves
Experimentally, liquidus and solidus curves can be determined by taking cooling curves at different compositions. -- for pure components, there is a sharp break in the cooling curve (thermal arrest) due to heat of transformation (crystallization). -- for two-component mixtures, heat is released over a range of temperatures T = (TL TS), so that there is a change in slope of the cooling curve.

Fig. 29 (a) A binary isomorphous phase diagram showing cooling curves for (b) pure component A, and (c) alloy 1.

Solidification and microstructure

Under equilibrium conditions, all compositions in an isomorphous system solidify in a similar manner.

Figure 30 Equilibrium solidification of alloy 1 (composition 0.6 B); (a) the cooling path and sketches showing the development of the microstructure, and (b) an expanded section of part (a) showing the compositions of the liquidus and solidus boundaries in the range of 1010C to 1060C.

-- at T1 the alloy begins to solidify, and the first solid crystallites to form have a composition given by the intersection of the horizontal T1 isotherm (tie line) with the solidus curve (xB = 0.70). -- when the temperature is reduced to T2, the compositions of both liquid and solid phases are given by the intersection of the tie line with the liquidus and solidus curves (xS = 0.68; xL = 0.57). -- similarly for T3, T4, and T5, until at T5 solidification is complete. -- the final result of solidification is a polycrystalline (many-grained) material. -- at all temperatures, the amounts of liquid and solid phases are given by the Lever rule.

Example
What are the mass fractions of solid and liquid phases in equilibrium at T2?

(0.68 0.60) = 0.73 p CL = = (p + q) (0.68 0.57 ) (0.60 0.57) = 0.27 q Cs = (1 CL ) = = (p + q) (0.68 0.57 )

Deviations from ideal behavior

The shape of the isomorphous diagram, Figure 27, reflects ideal mixing of the components A and B in both liquid and solid states. This means that the bond energies for A-B pairs must be equivalent to the average of the bond energies for A-A and B-B pairs, i.e. EAB = (EAA + EBB)/2. -- when EAB < (EAA+ EBB)/2, then the A component prefers B nearest neighbors and vice versa; thus, the favored arrangement is an ordered solution in which the number of A-B bonds is maximized. -- when EAB > (EAA+ EBB)/2, then the A component prefers As as nearest neighbors and the B component prefers Bs; thus, the favored arrangement is a clustered solution in which the number of A-B bonds is minimized. If the clustering tendency in the solid phase increases, relative to that of the liquid, a melting point minimum occurs, resulting in the formation of an eutectic phase diagram.

Eutectic system

Figure 31 A binary eutectic phase diagram and the associated terms used to describe regions of a eutectic system.

As in the isomorphous system, the boundaries separating the liquid and solid phase fields and the two-phase fields are called liquidus and solidus boundaries, respectively. -- the two liquidus curves converge at an eutectic point, E, which is the lowest melting point in the system -- at the eutectic point, the temperature and compositions of the two solid phases ( and ) are fixed. The invariant reaction may be represented as

where and are the terminal solid solutions of B in A (x1) and A in B (x2) at the eutectic temperature. Not present in an isomorphous system, solvus boundaries appear at both ends of the eutectic phase diagram, representing the temperature dependence of the solid solubility of each component.

L +

Solidification and microstructure

1. Eutectic composition

Fig. 32Schematic of the equilibrium microstructures for a Pb-Sn alloy of eutectic composition C3 above and below the eutectic temperature.

Fig. 33 - Photomicrograph showing the microstructure of a Pb-Sn alloy of eutectic composition. 375 x.

Fig. 34 - Schematic representation of the formation of the eutectic microstructure in the Pb-Sn system.

Eutectic microstructure consists of alternating layers (lamellae) of (dark) and (light) phases, where and are solid solutions of Sn in Pb and Pb in Sn, respectively -- microstructure is formed by counter-diffusion of Sn and Pb atoms just ahead of the advancing solid-liquid interface during solidification. -- scale of the eutectic microstructure decreases with increasing cooling rate from the liquid state.

The weight fractions of and phases at the eutectic point are given by the Lever rule.

C =

p (97.8 61.9) = 0.45 = (p + q ) (97.8 18.3)

C = (1 C ) = 0.55 2. Off-eutectic composition

Fig. 35 Schematic representations of the equilibrium microstructures for a Pb-Sn alloy of composition C4 as it is cooled from the liquid-phase region.

Fig. 36 Photomicrograph showing the microstructure of a Pb-Sn alloy of composition 50 wt.% Sn-50 wt.% Pb. This microstructure is composed of a primary Pb-rich phase (large dark regions) within a lamellar eutectic structure consisting of a Sn-rich phase (light layers) and a Pb-rich phase (dark layers). 400x. Off-eutectic microstructure (composition C4) consists of primary phase (formed during cooling through the semi-solid region) plus ( + ) eutectic (formed at the eutectic temperature, TE). -- just above TE, the weight fraction of primary phase is

C =

(61.9 C4 ) (61.9 18.3)

-- just below TE, the total weight fraction of phase (primary + eutectic ) is

C =

(97.8 C4 ) (97.8 18.3)

Cooling curves
Cooling curves can be used to determine the locations of eutectic point, liquidus curve, and solidus curve

Fig.37 The use of cooling curves to establish the liquidus and solidus in a binary eutectic alloy under equilibrium conditions.

Alloy 3 (eutectic composition) experiences a sharp break in the cooling curve, due to isothermal transformation of the liquid phase into two solid phases (+). Alloys 2 and 4 experience heat release over a range of temperatures T = (TL - TS), prior to isothermal solidification at the eutectic temperature, TE. Alloys 1 and 5 behave like regular solid solution alloys, in that there is a change in slope of the cooling curve at TL and TS.

Complex systems
Most practical phase diagrams are more complex than the relatively simple isomorphous and eutectic systems considered so far. Figure 38 shows a binary phase diagram that comprises: -- two eutectic reactions (L + ; L + ), a peritectic reaction (L + ), and an intermediate phase reaction (L ). -- phase melts congruently, i.e. the compositions of liquid and solid phases are the same. -- phase melts incongruently, i.e. it decomposes into two phases (L + ), such that composition of the liquid phase is different from that of the solid phase.

Fig. 38 (a) Complex phase diagram containing a peritectic and two eutectic reactions, and (b) invariant reactions in (a) emphasized along with their symbolic representations.

Eutectoid system
An eutectoid reaction is a solid-state reaction, involving the decomposition of a single solid phase () into two solid phases ( + ) having different compositions. -- decomposition occurs by solute redistribution in the phase just in front of the two phase ( + ) region. -- solid-state reaction is slower than liquid-state reaction, due to much slower diffusion rate in the solid state. -- most important commercial system that exhibits an eutectoid reaction is the Fe-Fe3C system

Fe-Fe3C system
Upon heating, pure Fe experiences two solid state reactions: 912C -ferrite (bcc)

1394C -austenite (fcc)

-ferrite (bcc

Fig. 39 The Fe-C phase diagram. With the addition of C, these polymorphic transformations are drastically modified -- the solubility of C in -austenite is large; maximum of 2.14 wt.% at 1147C. -- the solubility of C in -ferrite is small; maximum of 0.022 wt.% at 727C. -- when the solubility of C in and phases is exceeded, an intermediate phase Fe3C, known as cementite, makes its appearance.

Upon cooling from the fully austenitic state, an alloy of composition 0.76 wt.%C, the following eutectoid reaction occurs: (austenite)

+ Fe3C (ferrite) (cementite)

pearlite Pearlite is the product of -austenite decomposition, and consists of alternating layers (lamellae) of -ferrite and Fe3C-cementite. -- pearlite is nucleated at the prior austenite grain boundaries, and propagates by a diffusion controlled mechanism -- C atoms diffuse away from the -ferrite regions into the adjacent Fe3C cementite regions.

Fig. 40 Schematics of microstructures for an Fe-C alloy of eutectoid composition (0.76 wt.% C) above and below the eutectoid temperature.

Fig. 41 Photomicrograph of an eutectoid steel showing the pearlite microstructure, which consists of alternating layers of -ferrite (light phase) and Fe3Ccementite (dark phase). 500x

Fig. 42 Schematic representation of the formation of pearlite from austenite; direction of carbon diffusion indicated by arrows. The wt. fractions of the constituent and Fe3C phases in pearlite can be determined using the Lever rule.

wt. fraction =

(6.7 0.76) = 0.89 (6.7 0.022)

wt. fraction Fe3C = 0.11

Off-eutectoid composition
Alloy compositions to the left and right of the eutectoid (0.76 wt.% C) are termed hypoeutectoid and hypereutectoid, respectively. -- cooling a hypoeutectoid alloy from the fully austenitic region gives rise first to pro-eutectoid -ferrite (along the prior austenite grain boundaries) and then pearlite. -- similarly for hypereutectoid alloys, except that the pro-eutectoid phase is cementite. -- the weight fractions of pro-eutectoid ferrite and total ferrite (proeutectoid + eutectoid ferrite) can be determined using the Lever rule. Hypoeutectoid alloys comprise most of the commercially important steels, since they combine high strength (due to pearlite) and good fracture toughness (due to pro-eutectoid ferrite).

Fig. 43 Schematic of the microstructures for an Fe-C alloy of hypoeutectoid composition C0 (< 0.76 wt.% C), as it is cooled from within the austenite phase region to below the eutectoid temperature.

Fig. 44 - Photomicrograph of a 0.38 wt.% C steel having a microstructure consisting of pearlite and pro-eutectoid ferrite. 635x.

Effect of cooling rate

Slow cooling from the fully austenitic region gives pearlite (diffusioncontrolled transformation). (fcc) (austenite)

(bcc) (ferrite)

Fe3C (orthorhombic) (cementite)

pearlite -- composed of alternating layers of ferrite () and cementite (Fe3C), Fig. 41. -- formed by redistribution of C in the phase just ahead of the advancing two-phase ( + Fe3C) interface, Fig. 42. -- pearlite is strong and tough. Fast cooling from the fully austenitic region gives martensite (diffusionless transformation). (fcc) (austenite)

(bct) (martensite)

-- martensite has a needle-like morphology and is hard and brittle.

Fig. 45 Progress of athermal martensitic transformation in an Fe-1.8 wt.% C alloy after cooling to (a) 24C, (b) -60C, and (c) -100C. When heated, Fe3C begins to form as fine precipitates within the martensite needles. -- this has the effect of reducing hardness and increasing toughness, called tempering. When heated just below the eutectoid temperature for a long time (~10 hours), a relatively uniform distribution of coarse Fe3C particles is formed in an ferrite matrix. -- such a microstructure, called spheroidite, possesses moderate strength and good ductility.

Fig. 46 Microstructure of a tempered martensite (spheroidite) in a steel with 0.7 wt.% C.

Isothermal transformation diagram

The pearlite transformation is both temperature and time dependent, whereas the martensite transformation depends solely on temperature, not time. This difference in behavior can be represented conveniently on an isothermal transformation (IT) diagram.

Fig. 47 Schematic of an isothermal transformation (IT) diagram for a eutectoid steel. Curve A slow cooling gives 100% pearlite Curve B fast cooling (quenching) gives 100% martensite Curve C slow cooling to point X, followed by quenching, gives 50% pearlite + 50% martensite

Martempering
This is a commercially important quench-and-temper process: -- quench to a temperature just above Ms and hold to minimize thermal gradients that can lead to surface cracking -- quench again to ambient temperature to form 100% martensite -- reheat to tempering temperature to develop fine-scale Fe3C particles -- resulting tempered martensite has high strength and moderate ductility

Fig. 48 Schematic showing the cooling curve superimposed on IT diagram for martempering, or indirect quench process (with a temper step).

Fig. 47 Schematic of an isothermal transformation ( ) (IT) diagram for a eutectoid steel. g Indicates microstructural consequences of changing cooling rate from the fully austenitic region -- slow cooling forms pearlite l li f lit -- fast cooling forms martensite

Incubation period is characteristic of pearlitic transformation, since it occurs via a diffusion-controlled mechanism -- nucleation and growth initiated at prior austenite grain boundaries

Martempering
This is a commercially important quench-and-temper process: -- quench to a temperature just above Ms and hold to minimize thermal gradients that can lead to surface cracking -- quench again to ambient temperature to form 100% martensite q g p -- reheat to tempering temperature to develop fine-scale Fe3C particles -- resulting tempered martensite has high strength and moderate tempered martensite ductility

Fig. 48 Schematic showing the cooling curve superimposed on IT diagram for martempering, or indirect quench process (with a temper step).