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AAE  590:  
Mechanical  Behavior  of  Materials  
Lecture  25:  Polymer  Structure  

Molecular  Shape  

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Molecular  Shape  

In  terms  of  strength:  linear  <  branched  <  cross-­‐linked  <  networked  
Linear  and  branched  -­‐  bonding  between  molecular  chains  is  dominated  by  van  der  Waals  
Cross-­‐linked  and  Networked  -­‐  bonding  between  molecular  chains  is  controlled  by  Covalent  bonds  
 

Molecular  Shape  
Side  groups  have  HUGE  affect  on  
mechanical  properNes  as  they  
affect  bonding  and  rotaNon  

Saturated  -­‐>  all  single  bonds  of  side  groups  

Unsaturated  -­‐>  sNll  has  spots  for  addiNonal  
bonding  and  ability  for  double  bonds  to  form  

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Molecular  Weight  

Molecular  length  influences  the  mechanical  properNes  and  melNng  temperature  

Degree  of  PolymerizaNon  

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ClassificaNon  of  Polymers  

•  ThermoplasNc  polymers  
–  Generally  soX  and  ducNle  
–  SoXen  when  heated,  harden  when  cooled  
–  Degrade  by  heat  breaking  primary  bonds  along  chain  
–  Reversible  secondary  bonding  between  chains  
•  Thermose[ng  polymers  
–  Generally  hard,  strong,  and  bri\le  
–  Heavily  networked  or  crosslinked  
–  Permanently  hard  
–  Burn  before  melNng  (soXen)  
•  Elastomers  
–  Deform  to  very  large  strains  
–  Returns  to  reference  state  when  load  is  released  
–  Classified  as  either  lightly  crosslinked  thermosets  or  thermoplasNc  

Microstructure  

•  Metals:  
–  Well  defined  crystal  structure  
–  DeformaNon  Ned  to  defects:  
•  Vacancies,  DislocaNons,  Grain  Boundaries,  Twins,  etc.  
 
•  Polymers:  
–  IndisNnct  structure  
•  Crystalline  
•  Semi-­‐Crystalline  
•  Amorphous  
–  Hard  to  idenNfy  defects  
•  Makes  it  difficult  to  define  or  quanNfy  mechanisms  that  result  in  
plasNc  deformaNon  

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Microstructure  of  Polymers  

•  Crystalline  
–  RepeaNng  array  of  molecules  
–  Periodic  in  3  dimensions  
–  Long  range  order  
•  Semi-­‐crystalline  
–  Structure  contains  regions  of  both  crystalline  
and  amorphous  molecular  arrangements  
–  Contains  short  range  order  in  crystalline  region  
•  Amorphous  
–  No  repeaNng  array  
–  No  long  range  order  
–  “without  structure”  

DeformaNon  Map  for  Amorphous  Material  

Microstructure  figures  taken  from  Callister,  “Material  Science  and  Engineering  An  IntroducNon”,  5th  Ed,  Wiley  (2000).  
DeformaNon  map  figure  taken  from  T.H.  Courtney,  “Mechanical  Behavior  of  Materials”,  McGraw-­‐Hill  (1990).  

Copolymers  

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Crystallinity  

Polymer  CrystallizaNon  

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Polymer  CrystallizaNon  

Glass  TransiNon  Temperatures,  Tg  

in  degrees  Celsius  

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Increasing  free  volume  with  Tg  

Mechanical  ProperNes  

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PlasNcity  response  with  Tg  

Comparing  ProperNes  to  Metals  

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Comparing  ProperNes  to  Metals  

Cold  drawing  

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ElasNc  Response  of  Polymer  

Deforming  Semicrystalline  Polymers  

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A  closer  look  at  semicrystalline  plasNc  

deformaNon  

SNffening  Mechanisms  

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Strengthening  Mechanisms  

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Strengthening  Mechanisms  

Thermal  CharacterisNcs  

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Polymer  Structure  with  Tg  

RelaxaNon  
modulus  vs  temp  
for  amorphous  
Influence  of   polystyrene  
temp  on  σ-­‐ε   showing  5  
behavior  of   regions  of  
polymethyl   viscoelasNc  
methacrylate     behavior    

Dependence  of  
polymer  properNes  
(including  Tg/Tm)  
on  molecular  
weight    

Figures  taken  from  Callister,  “Material  Science  and  

Engineering  An  IntroducNon”,  5th  Ed,  Wiley  (2000).  

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