CH2213: Analytical Chemistry

Lecture -30
DSC Analysis: Polymers & Glassy Materials
Professor Manickam Jayakannan
Department of Chemistry
IISER Pune, INDIA
E-mail: [email protected]
Website: http://www.iiserpune.ac.in/~jayakannan/

Date: 20th April 2022

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 Phase Transition in Solid State

Highly Crystalline Solids Semi-crystalline Solids Liquid-crystals

q Metals q Synthetic Polymers

q Alloys q Inorganic Glass
q Organic Compounds q Highly viscus liquids
q Metal Complexes

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 Small Molecules
Normal Heat
Molten Liquid
Solid
Apply Cooling
ordered state Disorder state
Tc

∆Hc
Heat -ve Cooling
Cp ={dH/dT)p
Cool
Heating
+ve
∆Hm
Crystal Isotropic Tm
Temperature

∆G = ∆H - T∆S (for isolated and reversible transitions, ∆G = 0)

Entropy change, ∆S = ∆H/T in Kelvin scale
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 Glassy Systems

long-chain systems
Heat
Si {SiO2}n Molten Liquid
X
O Apply Cooling Apply
Cooling
Si O Si O Si
Ma
Inf Ap y be Glass q Intermediate state
O ini ply … q Kinetically trapped
slo tes
w i
Si
Co mall Amorphous state
oli y
ng (Disorder state)
Crystal lattices
(ordered state)

Physical nature of aliphatic hydrocarbons with increase in chain “n”

q Polyethylene Melting point = 130 deg C

q Gaining enormous mechanical strength
n
q Flexible, expandable, and low density
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 Glassy & Rubbery System: Polymers

Unit cell
Cool

Molten state Chain Folding 3D Spherulites

2D Lamellar
(Crystal-Growth)
(Nucleation)
Amorphous
domain Lamellae formation

Crystalline domain

q Reality: Interchain network in multiple-lamella

q Bulk: 100 % Crystallinity is not possible; but 100 % Amorphous is feasible
q Polymers are called Semi-crystalline
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 Glass Transition temperature

Liq.N2
Rubber
bands
Chains are immobile
(or)
Brittle Chains are highly mobile Water tubes
at low temperature Flexible at room temperature
(Glass-like state) Allow it warm (Rubber-like state)

-ve Glass transition temperature

ate
Cp ={dH/dT)p te t
sta
e r ys
sy bb
G las Ru
+ve Heating cycle

Temperature

Thermograms for Typical Amorphous polymers

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 DSC Thermograms for Amorphous polymers
1st Cooling Cycle
Exo

Tg

g io o n
Glassy state

Isothermal

Re dati
Heat

n
gra
flow
Tg

De
Endo

1st heating Cycle Glass Transition Rubbery state

Temperature

Temperature
q No molten state or phase transition occurs

O Tg = 156 deg C
O
n

Bisphenol-A Polycarbonate

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 Glass Transition temperature

Not Brittle
Pour hot (highly flexible)
Water
(Rubber-like state)
Chains are
immobile
(Glass-like state) Apply high
temperature
Melted
Keep it at
Thermograms for Typical Medium temperature
80-100 deg C
Semi-crystalline polymers

-ve Glass transition

temperature
Heating cycle
dH/dT ate
t
sys
+ve las
G Rubbery state Molten State

Temperature
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 DSC Thermograms for Crystalline polymers
Case-1: Regular trend: Melt Crystallization
TC

!HC

g io o n
Exo

Re dati
Tg

n
Heat

gra
flow Glassy state Rubbery state

De
Glass Transition
!HM
Endo

Temperature

supercooling
effect TM

Temperature

q TC will be always lower than TM

q TM – TC is caused by supercooling effect, tunable to cooling rate
q !HM will be always lower than !HC
q It is completely reversible process, !G=0; thus; !H = T!S