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Physical structure of polymers

Prof. Wendy Liu

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  1    
Last Time

20 mers 16 mers

10 mers
•  Number average molecular weight: M n = ∑ xi M i xi =
∑ Ni i

•  Weight average molecular weight M w = ∑ w M Ni M i

i i
wi =
∑ Ni M i
•  Degree of Polymerization DP =
•  Polydispersity index PDI = M w
BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  2    
apply  sample  
•  Filtration
–  Size – size exclusion chromatography
•  Gel permeation – organic solvent
•  Gel filtration – aqueous solvent Porous  Beads  
(silica,  polymeric)  
–  Charge
–  Affinity
•  Retention time depends on the SIZE of the
•  Large molecules cannot penetrate
pores, flow right through
•  Small molecules penetrate pores,
retained for a long time
•  Calibration with samples of known MW
fracDon  collector  

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  3    
Step growth polymerization
Reaction between functional groups (between monomers, or between
monomer and growing chain, or between two growing chains)

For a polymer to form, the monomers must be able to react at two or

more sites (at least bi-functional)

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  4    
Step growth (cont’d)
•  Formation of polymer requires more than 1 functional group on each

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  5    
•  Homopolymer – one type of monomer or repeating unit
•  Copolymer – more than one type of species

•  Like alloys for metals, copolymers often have superior properties

when compared to homopolymers

•  Random co-polymer: -A-B-A-A-B-A-B-B-B-A-A-B-

•  Alternating copolymer: -A-B-A-B-A-B-A-B-A-B-A-B-A-
•  Block copolymer: long sequences of each –A-A-A-A-A-A-B-B-B-B-B-
•  Graft copolymers:

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  6    
Polymer microstructure


Linear Branched Cross-Linked Network

•  Linear polymers – repeat units joined end to end in single chains. Chains are
generally flexible, can slide past one another. Examples include polyethylene,
polystyrene, poly(methyl methacrylate).
•  Branched polymers – side branch chains are connected to the main chains by
covalent bonds; packing density is reduced; high density polyethylene is linear
whereas low density polyethylene is branched.
•  Crosslinked polymers – adjacent linear chains are joined together by covalent
bonds. Crosslinking achieved during synthesis or afterwards. Rubbers often
have crosslinks.
•  Network – multifunctional monomers that form three or more covalent bonds.
Polyurethane, silicone are examples.

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  7    
•  Ordered atomic arrangements
involving molecular chains
•  Crystal structures in terms of
unit cells
•  Example shown
–  polyethylene unit cell

•  In general, polymers with bulkier

side chains, branched polymers,
atactic polymers are less likely
to form crystalline structures

Adapted from Fig. 14.10, Callister & Rethwisch 8e.

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  8    
Lamellar regions of crystallinity
•  Crystalline regions
–  thin platelets or lamella with chain folds at faces
–  Chain folded structure

10 nm

Adapted from Fig. 14.12, Callister &

Rethwisch 8e.

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  9    
Semi-crystalline polymeric materials
Polymers rarely 100% crystalline region
•  Difficult for all regions of all chains to
become aligned
•  Rate of cooling and polymer structure
determine crystallinity

Polymer chemistry influences crystallinity

- Linear
- Iso or syndiotactic polymers
- Alternating co-polymer
… are more likely to be crystalline

Adapted from Fig. 14.11, Callister 6e.

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  10    
Percent crystallinity
Degree of crystallinity expressed as % crystallinity and can be
described in terms of the density of the material.

ρc > ρ a Because  the  chains  are  usually  more  closely  packed  

ρc = Density  of  perfect  crystal  

ρc ( ρ s − ρ a ) ρ a = Density  of  totally  amorphous  
%xtal = ×100
ρ s ( ρc − ρ a ) ρ s = Density  of  specimen  

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  11    
•  Some semicrystalline
polymers form spherulite
•  Nucleation and growth

•  Alternating chain-folded
crystallites and amorphous
•  Spherulite structure for
relatively rapid growth rates

Adapted from Fig. 14.13, Callister & Rethwisch 8e.

BME111  Design  of  Biomaterials  Spring  2015    April  14    Lecture  5  Slide  12