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Thermoplastics have loose polymer chains that break
apart when heat is applied.
Thermosets have rigid, cross linked polymer structures
that once set with heat cannot be reshaped.
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Glass Transition Temperature (Tg)
• All polymers have a temperature by which the configuration changes
from a rigid or glassy state to a rubbery or flexible state.
• The temperature at which it occurs is called the “glass transition”
temperature. For instance, the glass transition temperature, or Tg, of
low-density polyethylene is − 100°C.
• Below that temperature, the plastic is rigid and hard.
• Above that temperature, the plastic is rubber.
• That is why at room temperature, polyethylene is flexible and can be
made into a rubbery produce or plastic bag.
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Glass Transition Temperature (Tg)
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Polymer Characterization
Molecular Mass: GPC, SLS, end group analysis, etc.
Molecular Structure: ultraviolet-visible spectroscopy,
infrared spectroscopy, Raman spectroscopy, nuclear
magnetic resonance spectroscopy, electron spin resonance
spectroscopy, and mass spectrometry
Morphology: TEM, WAXS, SAXS
Thermal properties: Tg, Tc, Tm
Mechanical and viscoelastic properties
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Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
heater heater
The DSC is heated at a constant rate (10 oC/min is
typical). The computer controls the temperature in
both sample holders by adjusting the amount of heat
flowing through the heater. Difference in the heat
flows going through both heaters indicates that the 12
sample is going through a transition.
Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
semi-crystalline
Heat flow
melt material melt
glass
Tg Tc
Tm
Temperature
Heat flow from DSC to sample
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Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
Tg: At Tg, local motion of the chains is enabled. For local
motion of the chains to be enabled, heat must be provided to
the sample (heat flows from DSC to sample: positive heat
flow). heater heater
Tc: When heated above Tg, the chains experience enough
freedom so that some of their parts can arrange themselves
into microcrystals. Crystallization releases heat. Heat flows
from sample to DSC: negative heat flow.
Tm: As the temperature increases further, the melting
Heat flow
temperature (Tm) is reached and the microcrystals melt. For
this to happen, the sample needs to absorb heat and heat flows
from DSC to sample: positive heat flow.
Transitions observed by DSC occur over a range of Tg Tc Tm
temperatures.
Temperature
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Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
Tg: At Tg, local motion of the chains is enabled. For local
motion of the chains to be enabled, heat must be provided to
the sample (heat flows from DSC to sample: positive heat
flow). heater heater
Tc: When heated above Tg, the chains experience enough
freedom so that some of their parts can arrange themselves
into microcrystals. Crystallization releases heat. Heat flows
from sample to DSC: negative heat flow.
Tm: As the temperature increases further, the melting
Heat flow
temperature (Tm) is reached and the microcrystals melt. For
this to happen, the sample needs to absorb heat and heat flows
from DSC to sample: positive heat flow.
Transitions observed by DSC occur over a range of Tg Tc Tm
temperatures.
Temperature
15
Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
Tg: At Tg, local motion of the chains is enabled. For local
motion of the chains to be enabled, heat must be provided to
the sample (heat flows from DSC to sample: positive heat
flow). heater heater
Tc: When heated above Tg, the chains experience enough
freedom so that some of their parts can arrange themselves
into microcrystals. Crystallization releases heat. Heat flows
from sample to DSC: negative heat flow.
Tm: As the temperature increases further, the melting
Heat flow
temperature (Tm) is reached and the microcrystals melt. For
this to happen, the sample needs to absorb heat and heat flows
from DSC to sample: positive heat flow.
Transitions observed by DSC occur over a range of Tg Tc Tm
temperatures.
Temperature
16
Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
Tg: At Tg, local motion of the chains is enabled. For local
motion of the chains to be enabled, heat must be provided to
the sample (heat flows from DSC to sample: positive heat
flow). heater heater
Tc: When heated above Tg, the chains experience enough
freedom so that some of their parts can arrange themselves
into microcrystals. Crystallization releases heat. Heat flows
from sample to DSC: negative heat flow.
Tm: As the temperature increases further, the melting
Heat flow
temperature (Tm) is reached and the microcrystals melt. For
this to happen, the sample needs to absorb heat and heat flows
from DSC to sample: positive heat flow.
Transitions observed by DSC occur over a range of Tg Tc Tm
temperatures.
Temperature
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Glass Transition
How would the DSC plot of a sample of atactic polystyrene look like?
Heat flow semi-crystalline
melt material melt
glass atactic
Tg Tc polystyrene
Tm
Temperature
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Glass Transition
The glass transition temperature (Tg) is the most important single
parameter that determines what a given amorphous polymer will
be used for.
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Question: Which polymer would you use to make a window?
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Question: Which polymer would you use to make a window?
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Question: Which polymer would you use to make a rubber band?
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Question: Which polymer would you use to make a rubber band?
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Question: Which polymer would you use to make a rubber band?
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Polyethylene is an interesting case. Its Tg equals −125 oC, yet PE is
sufficiently rigid to be used extensively for packaging applications.
Polymers structure Tg (oC)
Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
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Glass Transition
Polyethylene is an interesting case. Its Tg equals −125 oC, yet PE is sufficiently rigid to
be used extensively for packaging applications. The rigidity of PE is due to PE
microcrystals which bind the chain together and inhibit flow. Tm for PE equals
+120 oC.
Defects which hinder crystallization lower the rigidity of PE.
Thus high density polyethylene (HDPE) is more rigid than low density polyethylene
(LDPE).
DSC trace for polyethylene
Cp = Heat flow /
semi-crystalline
melt material melt
glass
Tg = −125 oC
Tc Tm = +120 oC
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