Chapter 1/2 Four Types of Materials and Order of their density: 1.

Metals Variable bond energy Strong, ductile Highly conductive (thermal, electrical) Opaque and reflective 2. Polymers/plastics Covalent bonding Soft, ductile, low strength Insulators Translucent or Transparent 3. Ceramics Ionic Bonding, some covalent. So large bond energy Compound of metallic and non-metallic elements Brittle/glassy Insulators 4. Biological materials (or Biomaterials) Covalent, hydrogen, ionic interactions, hydrophobic interactions, hydrophilic Flexible Programmable, smart selective 5. (Nanomaterials)

Density Orders: Metallic, Ceramic, Polymers, Biomaterials % Ionic Bonding:

Primary vs Secondary Bonding: 1. Primary bonds: a. Covalent b. Ionic c. Metallic 2. Secondary bonding: a. Hydrogen

b. Van der Waals c. Hydrophobic d. Hydrophilic Chapter 3 Metallic Crystals Densely packed, often crystal because homogeneous and non directional bonding Simple Cubic Structure (SC) Low density packing Only Po Coordination number = 6 APF = 0.52 1 atom/unit cell Body Centered Cubic Structure (BCC) Coordination number = 8 Atoms touch along cube diagonals 2 atoms/unit cell Cr, W, alpha FE, Tantalum, Molybdenum 4R = sqrt(3) * a (determine by drawing through 3d diagonal, 2d diagonal, and one side) APF = 0.68 Face Centered Cubic Structure (FCC) Coordination number = 12 Layered: 5, 4, 5 Al, Cu, Pb, Ni, Pt, Ag Coordination number = 12 4 atoms per unit cell APF = 0.74 4R = sqrt(2) * a (2 sides, 1 2d diagonal) Hexagonal Close packed structure Coordination number = 12 Layered 7,3,7 Cd, Mg, Ti, Zn APF = 0.74 Max C/A = 1.633 6 atoms per unit cell
( )

Ceramic Crystal Structure: Determined by cation/anion ratio, and maintenance of charge neutrality Coordination number increases as the ratio increases

AX2 Crystal Structures o Fluorite ABX3 Crystal Structure o Perovskite o BaTiO3

Crystallographic Systems: Directionality Algorithm (Vector -> index) 1. Reposition vector through origin 2. Read off projections in terms of unit cell dimensions a, b, c 3. Adjust to smalles integer values 4. Enclose in square brackets w/o commas, with overbars for a negative index Directions are crystallographically equivalent if the atom spacing along each direction is the same HCP Crystallographic Directions Drawing Algorithm 1. Remove Brackets 2. Divide by smallest integer so all values are greater than or equal to 1 3. Multiply by appropriate unit cell dimension a for a1/a2/a3 axes, c for z-axis 4. Construct vector by stepping off these projections Determining HCP Crystallographic Directiosn 1. Reposition vector to pass through origin 2. Read off in terms of 3 axes (a1, a2, and z) 3. Adjust to smallest integer values 4. Enclose in square brackets for three axis 5. Convert to 4 axis miller-bravais lattice with these equations 6. Adjust to smallest integer values and enclose in brackets

Miller Indices algorithm 1. Read off intercepts of plane with axes in terms of a, b, c 2. Take reciprocals of integers 3. Reduce to smalles tinteger values 4. Inclose in parenthese

Atomic Linear and Planar Density

Put length in terms of a, a should be given in problem

PD =

Common Techniques to Determine Crystal Structures o AFM: X-Ray Diffraction can be used to find the spacing between layers of materials Incoming X-Rays diffract from crystal planes, so at the critical angle the distance between the two rays can be found via d = (n*wavelength)/ 2sin(critical angle) Interplanar spacing for cubic species

h, k, l, are the indices of the parallel planes being considered

Polymers: Includes Wood, Cotton, Leather, Rubber, Wool Silk, Pitch

Can be classified via: 1. Condensation vs Addition Polymers 2. Step vs Chain Polymers 3. Thermoplastic vs Thermosetting Polymers

Addition (Chain) Polymers Formed via Initiation -> Propagation -> Termination with free radicals "Chaining" Examples: Polyethylene, Poly(vinyl chloride)/PVC, Poly(methyl methacrylate)/PMMA Criteria for Chain 1. Requires an initiator/catalyst 2. Can only add monomers to macro ions or macro radicals 3. Initiation has a large Ea, Propogation has a small Ea 4. Monomer concentration decreases vs time 5. Macromolecules are formed from the very beginning of the reaction 6. Average molecular weight doesn't vary with reaction time

Condensation (step) Polymers Formed by dehydration synthesis or other condensation o Precedes by adding together molecules one step at a time Examples: o Polyamide (H2N-R-NH2) o Protein/wood/silk (H2N-R-CO2H) o Polyester or PET HO-R-OH o Melamine-Formaldehyde (C-N=C in 6 member ring. Each C is bonded to an extra NH2) Criteria 1. No need for catalysts 2. All functional end groups can react 3. Ea is the same for every step 4. Monomer molecules disappear very quickly 5. Oligomers form very quickly, but long polymers only form towards end of reaction 6. Average molecular weight increases with reaction time

Bulk/Commodity Polymers Polyethylene PVC Polytetrafluoroethylene (PTFE) Polypropylene(PP) -CH2-CH(CH3)Polystyrene (PS) -CH2-CH(Benzyl) Poly(methyl methacrylate) or PMMA CH2C(CH3)(COO(CH3))Phenol-formaldehyde (Bakelite), Benzene ring with 3 methyle and one OH Poly(hexamethylene adipamide) Poly(ethylene terephthalate) PET Polycarbonate PC

Molecular Weight

= Sum( xi * Mi) xi = fraction of total number of chains with a particular molecular weight * the middle/mean molecular weight of that size range Mw = Sum(wi * Mi) o wi is the weight fraction of molecules within the same interval. Mi is the same. Degree of polymerization DP = Mn / m, m is the repeat unit molecular weight Polydispersity index PI = Mw / Mn o Measures breadth of the molecular weight o 1 means all equal length, only for natural proteins o 1.5 < PI < 5 is common for synthetic

Thermoplastic Polymers Linear and branched structures Soften when heated, harden when cooled Recycled

Thermosetting Polymers Crosslinked and networked Will not soften upon heating after they have hardened Cannot be recycled

Elastomers Intermediate between thermoplastic and thermosetting Some crosslinking Extensive elastic deformation

Thermal transition temperatures Tg = glass transition temperature Tm = melting temperature