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L4
• No polymer is completely crystalline
• Even the most crystalline polymers have lattice defect
regions containing unordered amorphous material.
S u
m
1 R Vu
1
− 0 =
Tm Tm H u
(
1 − 1212 )
V1
Vu: molar volume per RU
V1: molar volume of the diluent
Others: usual meanings
= 1 − exp(− kt n )
k: temperature dependent growth rate parameter
n: temperature independent nucleation index
generally
1 n 4
Fundamental
Thermodynamic
Relationships
Major Techniques:
Differential Thermal Analysis (DTA)
Differential Scanning Calorimetry (DSC)
Thermal Gravimetric Analysis (TGA)
Dynamic Mechanical Analysis (DMA)
Thermo-mechanical Analysis (TMA)
Thermal Analysis Techniques
Differential Thermal Analysis (DTA)
• the temperature difference between a sample and an inert
reference material, DT = TS - TR, is measured as both are
subjected to identical heat treatments
Sensors
• Pt/Rh or chromel/alumel
thermocouples sample reference
pan pan
• one for the sample and one for
the reference
• joined to differential
temperature controller inert gas
Furnace vacuum
• alumina block containing sample
and reference cells Pt/Rh or chromel/alumel
Temperature controller thermocouples
Applications:
• Characteristic temperatures identification
• Glass transitions
• Melting and crystallization behavior
• Heat of melting and crystallization
• Solid-liquid ratio
• Specific heat capacity & heat of reaction
• Reaction kinetics & reaction behavior
• Oxidative stability & thermal stability
Differential Thermal Analysis
Differential Thermal Analysis
Advantages:
Instruments can be used at very
high temperatures
Instruments are highly sensitive
Flexibility in crucible volume
/form
Characteristic transition or
reaction temperatures can be
accurately determined
Disadvantages:
Uncertainty of heats of fusion, DTA
transition, or reaction estimations
is 20-50%
Differential Scanning Calorimetry (DSC)
sample reference
pan pan
Sample holder
• Al or Pt pans
inert gas inert gas
Sensors vacuum vacuum
Furnace
• separate blocks for sample and reference cells
Temperature controller
• differential thermal power is supplied to the heaters to maintain
the temperature of the sample and reference at the program
value
Heat Flux DSC heating
coil
Furnace
• one block for both sample and reference cells
Temperature controller
• the temperature difference between the sample and reference is
converted to differential thermal power, dq/dt, which is supplied to
the heaters to maintain the temperature of the sample and
reference at the program value