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
