Chapter 4: Structure of crystalline solids Thermoplastic and Thermosetting

Metallic Crystal structures Thermosplastic: soften when heated, hardened when cooled, linear and branched structures
Face centered cubic crystal structure (FCC) (Coo Num = 12) Thermosetting: crosslinked and network polymers, wont soften when heated
- The crystal structure found for many metals has a unit cell of cubic geometry with atoms located at each of the Thermoset – harder, stronger and better domensional staility
corners and the centers of all the cube faces Copolymer
- a = 2R √ 2 (a = cube length)(R = atomic radius - Alternating two repeat ubits alternatechain positions
- Block identical repeat units are clustered in blocks along main chain
- coor Num = each atom has same number of neighbor atoms - Groft homopolymer side branches
- N = Ni + Nf/2 + Nc/8 (N=number of atoms per unit cell, Ni = interior atoms, Nf = face atoms, Nc = corner atoms - Random 2 different units randomly dispersed on chain
- N = 0 + 6/2 + 8/8 = 4
- Atomic packing factor (APF) = volumes of all atoms within a cell/total unit cell volume = 0,74
Degree of polymerization for copolymers : m = ∑ fjmj (fj – mole fraction, mj – molecular weight)
- Eg. Copper, Al, silver, gold Polymer crystals
Body centered cubic crystal structure (BCC) (Coo Num = 3)
- Cubic unit cell atoms at 8 corners and single at cube center
- a = 4R ¿ √ 3 (a = cube length)(R = atomic radius
- N = Ni + Nf/2 + Nc/8 = 1 + 0 + 8/8 = 2
Hexagonal close-packed crystal structure (HCP) (Coo Num = 12)
- hexagonal unit cell
- N = Ni + Nf/2 + Nc/6 = 3 + 2/2 + 12/6 = 6
- c/a = 1.6333 (c = height), APF = 0,74
Denisty computation-metals

ρ=nA /Vc N A (n=number of atoms, A= atomic weight, Na = 6.022x10^23, Vc = volume of unit cell)
Ceramic Crystal structures
Ionic Arrangement geometries
Cations (+) give up positive charged valence elctrons to nonmetallic anions (-)
Influence crystal structure 1. Magnitude of electron charge on each of comonent ions must be neutral Chapter 7: Diffusion
2. size of ionic radi of cation (rc) and anions (rA). (rc < rA) - Refers to material transport by atomic motion
Structure types - 2 requirements : 1. Must be a empty adjacent tile 2. Atom must have sufficient energy to break bonds
- AX : equal number of cations and anions - Num atom capale of diffusing increase, temp increase (increase in vibration energy)
1. Rock salt – Sodium chloride +MgO (1 center and 4 corners of cube-FCC) - 2 types
2. Cesium Chloride – 4 anions on corners, cation cube center o Interdiffusion/impurity – atoms of 1 metal diffuse into another, how to low concentrations
3. Zinc Blende – (ZnS) ions tetrahedrally placed o Self diffusion – pure metals, atoms exchanging position are of same type
- AmXp : charges on anions and cations are not the same (m != 1 and/or p!=1) (CaF2)(ZrO2) Diffusion mechanisms
- AmBnXp : more than one type of cation (BaTiO3) (perovskite crystal structure) Probability of interstitial > vacancy
Silicate ceramics Vacancy interchange of an atom from normal lattice position to adjacent vacant lattice position
- Silicates are materials primarily composed of silicon and oxygen Interstutial atoms migrate from an interstitial position to a neighboring one that is empty, diffuuse more rapidly
- Various arrangement of a SiO4 tetrahedron Hydrogen, carbon, nitrogen
- Silica/silicon dioxide (SiO2)
- 3 primary forms – quartz, cristobalite, tridymite Steady and non steady state Diffusion
- Simple silicates – Mg2SiO4 / layered silicates Steady state
Carbon Diffusion flux (J) = how fast diffusion takes place : J = M/At (M-mass/num atoms, t-time, A-area)
Diamond: metastable carbon polymorph at room temperature and atmospheric pressure. Mass in = mass out
Each carbon bonds to 4 others Ficks 1st law : thin metal plate, concentrations/pressuures of diffusing species on both surfaces are held constant, eventualy
Graphite:polymorph of carbon reaches a state where diffusion flux does not change.
Polymer crystallinity J = -D dc/dx  dc/dx (concentration gradient) = (Ca-Cb)/(Xa-Xb)
Polymer – semi, metals -crystallne, ceramics – totally crystalline or non-crystalline D = differential coeffesient, C-concentrations

ρc(ρs−ρa) x 100 (ps = density specimen, pa = density totally amorphous polymer, Non-Steady state
% crystallinity = Diffusion flux/concentration gradient at some point varies with time
ρs( ρc−ρa) Net depletion/accumalation of species:Ficks 2nd law: dc = D(d2c/dx2)

Degree of crystallinity depends on: (pc = density perfectly crystalline polymers) Factors that influence diffusion
1. Rate of cooling during solidification Diffusing species : magnituude of diffusing coeffcient is indicative of rate at which atoms diffuse
2. Chain configuration Diffusing species and host material influuence the diffusion coeffecient
Most network and crossinked polymers are totally amorphous because the crosslinks prevent the polymers chains from Temperature : temperature has a large impact
realigning into crystalline structures Large Qd results in small D: D = Doexp(-Qd/RT)
Hydrocarbon groups Do – temp independent pre-exponential [m2/s], Qd – activation energy, R = 8,31, T-temp
1. Alcohols
Chapter 5: Structure of polymers
Hydrocarbon molecules (CnH2n+1) Dislocations + Plastic deformation
- Composed of hydrogen and carbon 2. Ethers Edge dislocations localized lattice dislocation exists along end of extra half plane of atoms
- Intramolecular bonds are covalent - Same sign, same slip plane = pull apart
- Unsaturated -molecule with double/triple covalent bonds
- Saturated-all bonds are single 3. Acids - Oppsoite sign, same slip plane = attrack
Methane(CH4) Ethane(C2H6) propane (C3H8), but, pen, hex Screw dislocations resulting from shear distortion
Pastic deformation = motion of large numbers of dislocations, process = slip
4. Aldehydes Slip system
Slip plane – densist atomic packing plane
Slip direction – direction of plane with most closely packed atoms
Isomerism- same composition with different atomic arrangements 5. Aromatic hydrocarbens Slip in single crystals
Polymer molecules
Composed of macromolecules which is composed of structural Entities called repeat units
Monomer – small molecule from which a polymer is synthesized
Chemistry of Polymer molecules

Mechanisms of strengthening in metals

Eg. Tetrafluoorethyiene monomer – polytetrafluoorethylene Grain size reduction
Vinylchloride monomer – poly vinylchloride (PVC) - Adjacent grain have different crystallographic orientations and common grain boundary
Homopolymer: When all of the repeating units along a chain are of the same type. - Dislocation takes place over boundary
Copolymer: Chains that are composed of two or more different repeating units. - Ability of metal to deform plastiacally depends on ability of dislocations to move
Functionality: The number of bonds that a given monomer can form. (Bifunctional- two active bonds, trifunctional- three - Restricting dislocation = harder / stronger material
active bonds etc.). - Fine grained = harder than coarse grain (greater grain boudary)
Moleculare weight
- Yield strength varies with grain size according to Hall-Petch Equuation
- Polymers with large chains have large molecuular weight
- Number average molecular weight = Mn = ∑ MiXi Solid solution
- Mi = middle moleculare weight of size i, Xi = fraction of total number of chains - Increases material’s strength at cost of decrease in ductility
- Weight average molecular weight = Mw = ∑ Mi W i - Involves alloying metals with impurity atoms that go into either substitutional or interstitial solid solution
- Concentration of impurity increases, yield and tensile strength increases
- Mi = middle moleculare weight of size i, Xi = weight fraction of molecules in site - Impurity atoms result in restriction of dislocation movement
- Small impurities exert tensie strain on surrounding atoms

- Large mpurities exert compressve strains on surrounding atom

Strain hardening
- Phenomenon occurs when ductile metal becomes stronger and harder as it deforms plastiaclly
- Also called cold working/ work hardening

Moleculare shape - Strain hardening affects can be removed bby annealing heat treatment
Molecular entanglement accurs when chainasuume twisted coiled and kinked shapes to chain bond rotation - Dislocation density increases, deformation increases, results in disloaction multiplies
Rotation flexibility is diminished when 1. Double chain bonds are present 2. Bulky side groups are part of repeat unit - Dislocation density decreases = resistance to dislocation motion increases to other dislocations
Moleculare structure Recovery
1. Linear polymer repeat units are joined together end-to-end in single chains - Absence of externally applied stresses
2. Branched polymer side branch connected to main ones - some of stored internal strain energy is relieved by dislocation motion
(Side branches reduce packing effiency – lower density) - physical properties recover to pre-strain-hardened states
3. Crosslinked polymers adjacent linear chain are joined together at various positions (covalent bonds) Recrystallization
(achieved during synthesis or y non-reversible chemical reaction) - refers to formation of new set of equiaxed (equa dimensions in all directions) and strain free grains
4. Network polymers multifunctional monomeric forming 3 or more active covalent bonds – 3D - metal becomes weaker softer and more ductile
Moleculare configerations - used to refine grain structure of cold-worked metals
Head-to-tail and head-to-head - low dislocation densities
- Stereoisomerism situation in which atoms are linked together in the same order (head to tail) but differ in - new grains form small nuclei and grow until parent material us completely consumed
their spacial arrangement - extend of recrystallization = time and temp
o Isotactic – R groups on same side - recrystal temp depends on 1. Amount prior cold work 2. Purity of alloy
o Syndiotactic – R groups on alternative sides - CW increases, rate od crystallization increases, crystallization Temp decreases
o Atactic – random positioning - Pure metals = recrystallization more rapid
- Geometrical isomerism possible in repeat unit having a double bend between chain carbon atoms Grain growth
o Cis – CH3 group and H atom are positioned on same side as double bond - Refers to strain free grains if specimen is left at elevated temperatures
o Tians – CH3 and H on opppsoite site of double bond - Does not need to be preceeded by recovery or recrystallixation
 - Total grain boundary area decreases, grains grow

Phase diagrams