MT 271

Topic 2

Classes of Materials
Structure, Properties, Characterization
 Types of Materials

Solids are-
• Metals
• Polymers
• Ceramics
• Composites

Classified by type of bonds: chemistry and structure

 Inter-atomic bonding
Primary (stronger) bonds-
• Ionic bonds
• Covalent bond
• Metallic bond

Secondary (weaker) bonds-

• Hydrogen bonding
• Van der Waals bonding
 Bond strength
Heat of vaporization (KJ/mol)
Van der Waals He 0.14
N2 13

Hydrogen Phenol 31
HF 47

Metallic Na 180
Fe 652

Ionic NaCl 1062

MgO 1880

Covalent Diamond 1180

SiO2 2810
 Ionic bonding
• Transfer of electrons between a
cation (metal) and an anion (non-
metal)
• Columbic charge interactions
• Orderly arrangement of cations and
anions to form crystals:
fcc, bcc, hcp
• Examples: NaCl, MgO
• Results in low electrical and head
conductivity and low chemical
reactivity.
 Covalent bonding

• Typically seen in Si and C

• Bonding through electron sharing
• e.g., diamond and graphite
 Metallic bonding
• Metal atoms arranged in periodic arrangements
• Positive ion cores in a sea of electrons
– Free valence electrons which can "travel" about the material.
– Electrical charge is neutralized on average.
– Bonds are non-directional (isotropic): allows plastic deformation
– Atom position is non-discriminative: good electrical/ thermal conductance
 Weak bonds
Van Waals bonds:
– Form among hydrogen, oxygen and other atoms.
– Not directional.
– High number of possible bonds results in strength.

Hydrogen bonds:
– Formed when hydrogen is covalently bonded to an electronegative
atoms

Particularly important for polymers

 Classes of Materials

Solids are-
• Metals
• Polymers
• Ceramics
• Composites- some combination of the above
 Metals

• Metallic bonding
• Alloys are mixtures of metals
 Ceramics
• Solid inorganic compounds
• Combination of ionic and covalent bonding
• Examples: Al2O3
• Carbon: Diamond, Graphite
• Inorganic glasses: rapid cooling of molten
ceramic; lack long-range order

Structure of the ideal

YBa2Cu3O7 lattice.
 Polymers
• C atoms linked covalently in a chain-like arrangement
• Linear polymers; can be melted and re-melted: thermoplastics
• Chains in thermoplastics held together by van der Waals forces and
hydrogen bonds
• Branched side chains covalently cross-linked: thermosetting polymers

a) linear
b) branched
c) crosslinked
d) network
Mechanical properties of materials

• Tension
• Compression
• Torsion
• Shear
• Creep
• Fatigue
• Wear
 Elasticity

• Hooke’s law: strain (extension) proportional to stress (load), in elastic range

• Stress: force applied per unit area
• Strain: elongation per unit area of the original length
Tension and compression

Loading direction is
perpendicular to direction of
area supporting the load

Strain:
 Elastic modulus

Tension: Young’s modulus

 Shear

Load is applied parallel to the

area supporting it

Shear stress: t
Shear strain: g
 Shear modulus

Shear modulus =
shear stress/ shear strain
 Tensile/ compression testing

Uniaxial tension/ compression

testing instrument
 Brittle fracture and
plastic deformation

Brittle fracture: hard alloys, ceramics, Ductile fracture: metals and alloys
PMMA , graphite
Irreversible re-arrangement of atoms
Small stretching of inter-atomic bonds
 Fatigue

Failure at a stress lower than ultimate

tensile strength due to cyclic loading

Important for prosthetic heart valves,

pacemaker leads
 Surface properties of materials

The first interaction of material and biology is at the interface/ surface.

Phase: is a region of material that is chemically uniform, physically

distinct, and (often) mechanically separable

Surface: The outermost region of a material that is chemically and/ or

energetically unique by virtue of being located at a boundary.
NOTE: “chemically and/ or energetically unique”, not defined by
thickness/ distance

Interface: is the boundary region between any two phases

 Surface vs. Interface
Similar but distinct as generally accepted in surface science literature
A surface refers to an interface when one of the contacting phases is
vacuum

Interfaces:
e.g., solid against a vapor = (sv)
solid against a liquid = (sl)
liquid against a vapor = (lv)
solid against a solid = (ss)

Surface (against vacuum)

e.g., Solid against vacuum= (s)
 Surface is chemically reactive

Prone to reaction
Prone to contamination
More surface/volume in nanomaterials
Surface can rearrange in response to the environment
Surface depth: 1 nm for Au to 10 nm for polymers
 How do surfaces differ?

A- Rough vs. smooth

B- Different chemistry
C- Uniform vs. Phase separated/ patterned
D- Gradual surface vs. step (film)
E- ordered vs. random
F- crystal orientations
 Surface characterization methods

bonds-

Characterization tool can alter the surface- generate artifacts

Depth measured is different
Cost of equipment
Surface water-wettability
Forces determining water-wettability
Cohesive forces: Attraction of one molecule with its OWN kind
(liquid-liquid interactions)
Adhesive forces: Attraction of one molecule with the OTHER kind
(liquid-solid interactions)

Surface tension (g ): cohesive forces in

liquid at the surface give rise to surface
tension; liquid can resist an external force

g for water (at 25°C) = 72 dynes/cm

It takes 72 dynes of force to break a surface
film of water 1 cm long.
 Water contact angle
Water contact angle is the interplay of cohesive and adhesive forces

Young equation:

 is the contact angle

g is the interfacial tension for sv, sl, lv interfaces
Contact angle goniometry
Measuring contact angle
ESCA/ XPS
Electron spectroscopy for chemical analysis (ESCA)
X-ray photoelectron spectroscopy (XPS)
 Principle of ESCA
Photo-electric effect: X-ray causes emission of core electrons
BE = hn- KE
Binding energy
Kinetic energy: measured in the instrument
hn, the energy of the X-ray: input known
 ESCA spectra

bonds-
 SIMS
Secondary ion mass spectrometry (SIMS)
Surface bombarded with accelerated ions to sputter (secondary) ions
Measures mass of the emitted ions
 IR spectroscopy
Interaction of IR light with matter
Molecules absorb at characteristic resonant frequencies

Self-study: FTIR- why need “FT”??

 FTIR spectroscopy
Fourier transform infrared (FTIR)
spectroscopy

Identification of chemical structure

using atomic and molecular
vibrations

Difficult to separate bulk and surface

signals: surface FTIR methods

Fig A: attenuated total reflectance IR

(ATR-IR)

B: IRAS

C: Diffuse reflectance
 FTIR spectra example

FTIR spectra of MWNT, MWNT–CS and MWNT–CS–PC where-

MWNT = multi-walled carbon nanotube
CS = chitosan
PC = Phycocyanin (a dye)
 SEM
Scanning electron microscopy (SEM)
Focus and raster a high energy electron beam
Low energy electron emitted from the surface collected using a detector to
image for topography and atomic composition
Non-conducting materials (polymers) must be coated with metal

Self study on modes: Secondary electrons; Backscattered electrons; X-rays

 Scanning tunneling microscopy

STM image of a Au surface

STM uses quantum tunneling to generate an atom-scale, electron density

image of a surface
Limited to conducting/ semi-conducting materials
 AFM microscopy

The AFM records the deflection

of a tip mounted on a flexible
cantilever arm due to van der
Waals and electrostatic
repulsion and attraction
between an atom at the tip and
an atom on the surface.

Atomic-scale measurements of
cantilever arm movements
made by reflecting a laser
beam off a mirror on the
cantilever arm.
 Scanning probe microscopy
Imaging by physically scanning the surface with a fine probe.
Many types-
• AFM, atomic force microscopy
• BEEM, ballistic electron emission microscopy
• CFM, chemical force microscopy
• C-AFM, conductive atomic force microscopy
• ECSTM electrochemical scanning tunneling microscope
• EFM, electrostatic force microscopy
• FMM, force modulation microscopy
• FOSPM, feature-oriented scanning probe microscopy
• KPFM, kelvin probe force microscopy
• MFM, magnetic force microscopy
• MRFM, magnetic resonance force microscopy
• NSOM, near-field scanning optical microscopy (or SNOM, scanning near-field optical microscopy)
• PFM, Piezoresponse Force Microscopy
• PSTM, photon scanning tunneling microscopy
• PTMS, photothermal microspectroscopy/microscopy
• SCM, scanning capacitance microscopy
• SECM, scanning electrochemical microscopy
• SGM, scanning gate microscopy
• SHPM, scanning Hall probe microscopy
• SICM, scanning ion-conductance microscopy
• SPSM spin polarized scanning tunneling microscopy
• SSRM, scanning spreading resistance microscopy
• SThM, scanning thermal microscopy
• STM, scanning tunneling microscopy
• STP, scanning tunneling potentiometry
• SVM, scanning voltage microscopy
• SXSTM, synchrotron x-ray scanning tunneling microscopy