CHAPTER

3
Physical Properties
of Biomaterials

3.1 Introduction: From Atomic Groupings to Bulk Materials

Metals and Ceramics: Polycrystalline materials (interactions of multiple crystals)

Amount and type of dislocations

Polymers: Crystalline and amorphous regions (% Crystallinity)

Thermal transition of physical properties

3.2 Crystallinity and Linear Defects

point defects, linear defects, planar defects

3.2.1. Dislocations
(1) Edge dislocations

half-plane
dislocation line

magnitude and direction of

atomic displacement

atomic circuit drawing

Burger’s vector
(2) Screw and mixed dislocations

Screw dislocation: shear force ---- helical pattern

Mixed dislocation: Edge + Screw

(3) Characteristics of dislocations

a) localized lattice strains

b) relationship between the Burger’s vector and the dislocation line
c) invariant Burger’s vector
d) termination of dislocation
e) slipping of dislocations (slip planes)
3.2.2. Deformation

plastic (permanent) deformation [dislocation glide]

dislocation glide: planes with higher atomic density
slip and slip plane
dislocation’s geometry plane = crystallographic slip plane

slip system: crystallographic planes x # of slip directions

high --- more deformable (ductile), low --- little deformation (brittle)
Ceramics
limited movement
electroneutrality requirement
longer Burger’s vector
less slip --- brittle ceramics

3.3. Crystallinity and Planar Defects

planar defects: surface and grain boundaries

3.3.1. External surface

atoms at the surface --- no maximum coordination --- higher energy [surface tension]
---- thermodynamic instability ---- chemical reaction at the surface

3.3.2. Grain boundaries

metals and ceramics: polycrystalline

atoms at grain boundary --- no optimal coordination
---- higher energy ---- higher chemical reactivity

total interfacial energy: low in materials with larger grains

Two types of grain boundaries
(1) small-angle grain boundary
tilt boundary (edge dislocations), twist boundary (screw dislocations)
(2) high-angle grain boundary
severe misalignment [atomic mismatch ---- energy increase]

cf) twin boundary

3.4 Crystallinity and Volume Defects

volume defects: precipitates and voids

voids (pores): 1) accidental formation, 2) creation with porogens and fibers

porogens:
1) solid porogens [salts, gelatin (collagen), waxy materials (lipids or paraffin)]
---- extraction --- pore formation
extraction methods
amount and shape --- porosity and pore geometry
2) gaseous porogens
N2, CO2 / liberation and bubbling
amount, rate, timing of gas introduction --- porosity and pore geometries
fibers:
fiber size and packing density --- porosity and pore geometry

advantages: 1) exchange of fluids and gases, 2) tissue ingrowth & implant anchoring
3) tissue engineering applications
disadvantages: 1) decrease in mechanical strength,
2) altering biodegradation and corrosive properties

% porosity must be optimized

3.5 Crystallinity and Polymeric Materials

physical property of polymer ---- % crystallinity

3.5.1. % Crystallinity
chemical structure of mer and polymer’s configuration

factors:
1) mer side groups
2) chain branching
3) tacticity
4) regularity of mer placement
in copolymer
side groups:
large and bulky
branched vs. linear

location of side groups

tacticity
block copolymer

% crystallinity : density
3.5.2. Chain-folded model of crystallinity

Basic unit of polymer crystalline structure: Lamella structure

cf.) polymeric crystal’s unit cell
Real situation
1) several polymer chains per each lamella
2) single chain between lamella structure and interface
3) amorphous regions separating lamellae
4) intermingled chains

Spherulite formation
three dim. radial arrangement of lamellae
impingement upon growth
3.5.3. Defects in Polymer Crystals

(1) Linear defects

(2) Planar and Volume defects
planar defects: boundaries between spherulites
volume defects: void formation

3.6 Thermal Transition of Crystalline and Non-crystalline Materials

thermal transition of biomaterials ---- viscosity and material deformation

3.6.1. Viscous flow

crystalline materials --- plastic deformation

non-crystalline materials --- viscous flow
rate of deformation & applied stress

viscosity: material’s ability to resist deformation (handle-ability)

water; caramel; glass

3.6.2. Thermal transition
(1) Metals and crystalline ceramics
T > Tm: liquid and viscous flow
T < Tm: solid --- crystal structure and grain boundaries
(2) Amorphous ceramics (Glasses)
T>Tm: liquid state
Tm: temp with viscosity of 100 P
Tw: temp with glass viscosity of 104 P
T<Tg: solid state (glass)
(3) Polymers
liquid (rubbery solid) & glass
Tm and Tg
Crystalline polymers
T>Tm: random ordering of chains with no repeating structure
[translational motions]
Tm>T: highly ordered crystals

secondary bonds and Tm

1) degree of branching --- Tm 감소
2) molecular weight --- Tm 증가
Amorphous polymers
T>Tg: rubbery elastic materials
T<Tg: glassy and brittle polymer
[Tg<Tm] --- 1.4 < Tm/Tg < 2.0 for polymer

chain vibration and rotation

1) chain flexibility
2) chemical constituents
[bulky side groups, polar groups, high mol. wt., X-linking]
Polymers to be crystallizable
Tg< Tc <Tm
temp increase --- polymer chains with energy
--- highly ordered crystalline state [exothermic process]
--- disruption of the crystal structure

polymer annealing

degree of crystallinity

3.7 Techniques: Introduction to Thermal Analysis

Temp analysis; measurement of the physical properties of a material as a function

of temperature
TGA (thermogravimetric analysis)
DMA (dynamic mechanical analysis)
DSC (differential scanning calorimetry)
3.7.1. Differential Scanning Calorimetry
(1) Basic principles

power-compensated DSC
heat-flux DSC

(2) Instrumentation

furnace/DSC sensors/ processor

(3) Information provided

Tg: heat capacity

Tm: peak temp
% crystallinity