Chapter 3 CRYSTAL SYSTEMS Cont

Linear Density (LD)

Related to directional equivalency eg. <100> Linear Density (LD) defined as number of atoms per unit length whose centers lie on the direction vector for a specific crystallographic direction

Number of atoms centered on direction vector LD Length of the direction vector

LD for FCC Unit Cell

z

Radius of the atoms: R

y
x

[110] Direction

LD

Number of atoms centered on direction vector Length of the direction vector

LD110

2 1 4R 2 R

Planar Density (PD)

Related to planar equivalency eg. {111} PD is defined as the number of atoms per unit area that are centered on a particular crystallographic plane

Number of atoms centered on a plane PD Area of the plane

Planar Density for FCC Unit Cell

z
4R

2R2

(110) plane

Number of atoms centered on a plane PD Area of the plane

2 1 PD 4R * 2R 2 4R2 2

Crystalline and Non-Crystalline Materials

Si
O

Crystalline SiO2 atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers Amorphous or Non-Crystalline SiO2 atoms have no periodic packing occurs for: -complex structures -rapidly cooled structures

Single Crystals and Poly Crystals

Single Crystals

Properties vary with direction Anisotropic E for BCC iron

E E

diagonal

Polycrystals

edge

= 273 GPa = 125 GPa

(collection of many grains)

Properties may / may not vary with direction If grains are randomly oriented, ISOTROPIC If grains are textured, ANISOTROPIC

Isotropy and Anisotropy

Isotropy: Measured properties (elastic modulus, conductivity, refractive index) independent of direction of measurement

Structurally symmetric crystals display isotropic behavior (cubic)

Anisotropy: Directionality of properties change with direction of measurement

Changes in atomic or ionic spacing with crystallographic direction (Refer Table 3.7) Increases with decreasing symmetry Triclinic structures very anisotropic

Determining Crystal Structures

Sir William Bragg Lawrence Bragg Father-son shared Nobel prize in Physics in 1915

Analysis of crystal structures using X-rays William Bragg in charge of research on the detection and measurement of underwater sounds in connection with the location of submarines

X-Ray Diffraction for crystal structure

Diffraction

2 waves that mutually reinforce One another Waves in phase

Scattering Event

A wave encounters regular spaced objects that scatter it Obstacle spacing is similar in length to the wavelength

2 waves that cancel One another Waves out of phase

Scattering Event

X-Ray Diffraction to determine crystal structures

S Q

dhkl (interplanar spacing)

Path length difference between 2 waves = SQ + QT Braggs law says that

the path difference = order of reflection (n) * wavelength ()

n needs to be a whole no.

Hence, SQ + QT = n = 2 dhkl sin

Braggs law

Applicable when waves interfere constructively When Braggs law not satisfied, waves interfere destructively, resulting in a low intensity diffracted beam Interplaner spacing for cubic structures,

d hkl

a h2 k 2 l 2

a is the lattice parameter (unit cell edge length) h, k, l are Miller indices Similar complex relations exist for other six crystal systems

X-Ray Diffraction Measurements

Chapter 4

POLYMER STRUCTURES

Polymers

Naturally occurring

Wood, rubber, cotton, wool, leather Proteins, enzymes, starches, cellulose

Synthetic (from organic molecules)

Plastics, synthetic rubbers, Fibers

Polymer Structures
ISSUES TO ADDRESS...
What are the general structural and chemical characteristics of polymer molecules?

What are some of the common polymeric materials, and how do they differ chemically?
How is the crystalline state in polymers different from that in metals and ceramics ?

16

Hydrocarbon molecules

Most polymers are organic in origin Many organic materials are hydrocarbons

Covalent bonds Each C has 4 electrons that may participate in covalent bonding Single electron pair sharing single bond

Polymer Composition

Saturated hydrocarbons Each carbon singly bonded to four other atoms Example: Ethane, C2H6

H C C

18

Unsaturated Hydrocarbons

Double & triple bonds somewhat unstable can form new bonds

Double bond found in ethylene or ethene - C2H4

H C C H

H H

Triple bond found in acetylene or ethyne - C2H2

H C C H
19

Isomerism

Isomerism two compounds with same chemical formula can have quite different structures for example: C8H18

normal-octane
= H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H H H H H H H H H C C C C C C C C H H H H H H H H H

H3C ( CH2 ) CH3

6

2,4-dimethylhexane
CH3 H3C CH CH2 CH CH3 CH2 CH3
20

Polymer Molecules

Much larger in comparison to the hydrocarbon molecules Macromolecules A chain of carbon atoms is the backbone Mer The repeating unit in a polymer chain Monomer a stable unit from which the polymer is synthesized

Polymerization and Polymer Chemistry

Free radical polymerization

H H R + C C H H monomer (ethylene) H H + C C H H H H R C C H H initiation

free radical

H H R C C H H

H H H H R C C C C H H H H

propagation

Initiator: example - benzoyl peroxide

H H H 2 H H C O H
22

dimer

C O O C

=2R

Chemistry of Polymer molecules

H H

C C
H H

Monomer

Types of Polymers

Homopolymer

All repeating units along a chain are of the same type; polymer formed from a single monomer Eg. polyethylene, formed by polymerization of ethylene 2 or more different mer units involved PMMA

Copolymer

Polymer Chains

Polyglycolic acid and Poly Lactic acid Fiber of Kevlar

Bulk or Commodity Polymers

26

Bulk or Commodity Polymers (cont)

27

Bulk or Commodity Polymers (cont)

28

VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions

29