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Heat Flow
0 .0 -0 .1
Endothermic: heat flows into the sample as a result of either heat capacity (heating) or some endothermic process (glass transition, melting, evaporation, etc.)
-0 .2
-0 .3
-0 .4
0
E xo U p
25
50
75
100
125
150
T e m p e ra tu re ( C )
0 .1
Heat Flow
0 .0
Exothermic: heat flows out of the sample as a result of either heat capacity (cooling) or some exothermic process (crystallization, cure, oxidation, etc.)
0 20 40 60 80 100 120 140 160
-0 .1
E xo U p
Te m pe rature (C )
Temperature
What temperature is being measured and
displayed by the DSC? Sensor Temp: used by most DSCs. It is measured at the sample platform with a thermocouple, thermopile or PRT.
Sample Platform Chromel Area Detector Reference Platform Constantan Body Thin Wall Tube
Temperature
What temperature is being measured and
displayed by the DSC? Pan Temp: calculated by TA Q1000 based on pan material and shape Uses weight of pan, resistance of pan, & thermoconductivity of purge gas What about sample temperature? The actual temperature of the sample is never measured by DSC
Temperature
What other temperatures are not typically
being displayed. Program Temp: the set-point temperature is usually not recorded. It is used to control furnace temperature Furnace Temp: usually not recorded. It creates the temperature environment of the sample and reference
dH dT = Cp + f (T, t) dt dt
dT = Heating Rate dt
f (T, t) = Heat flow that is function of time at an absolute temperature (kinetic)
Besides the three temperatures (Ts, Tr, T0); what other values do we need to calculate Heat Flow? How do we calculate these?
T0
1 T 1 dTs d T q= + T0 + (Cr Cs ) Cr Rr d d Rs Rr
s
Cs
Rr =
r
Cr
0.04
50
50
0.03
0.03
40
40
0.02
0.02
This cell is very well balanced. It is acceptable and usual to have larger differences between sample and reference.
30 -200 -100 0 100 200
0.01 300
Temperature (C)
0.4
0.2
0.0
-0.2
-0.4 -100
100
200
300
400
Temperature (C)
Q100
Q10
Cleaning Cell
If the cell gets dirty
Clean w/ brush Brush gently both sensors and cell if necessary Be careful with the Tzero thermocouple
Sample Shape
Keep sample thin Cover as much as the bottom of pan as
possible
Sample Shape
Cut sample to make thin, dont crush If pellet, cut cross section
Sample Shape
Cut sample to make thin, dont crush If pellet, cut cross section
Good
Bad
Sample Size
Larger samples will increase sensitivity
but. Larger samples will decrease resolution
Sample Size
Sample size depends on what you are
measuring If running an extremely reactive sample (like an explosive) run very small samples (<1mg) Pure organic materials, pharmaceuticals (1-5mg) Polymers - ~10mg Composites 15-20mg
Size: 1.2100 mg
-5
Size: 0.4900 mg
-10
Size: 5.7010 mg
-15
-20
-25 150
Temperature (C)
Purge Gas
Purge gas should always be used during DSC
experiments Provides dry,inert atmosphere Ensures even heating Helps sweep away any off gases that might be released Nitrogen Most common Increases Sensitivity Typical flow rate of 50ml/min
Purge Gas
Helium
Must be used with LNCS High Thermo-conductivity Increases Resolution Upper temp limited to 350C Typical flow rate of 25ml/min Air or Oxygen Used to view oxidative effects Typical flow rate of 50ml/min
Start-up Hook
12
9 .5 6 m g P E T @ 1 0 C /m in
10
-0 .0 5
-0 .1 5 4
-0 .2 5 -5
E xo U p
0 5 15 25 35
Te m pe ra ture (C )
D o no t a tte m pt to inte rpre t tra nsitio ns be fo re H e a ting ra te ha s sta bilize d Heat Flow (W/g)
Heating Rate
Faster heating rates increase sensitivity
but. Faster heating rates decrease resolution
PMMA 10.04mg
Thermal History
The thermal history of a sample can and will
affect the results The cooling rate that the sample undergoes can affect :
Crystallinity of semi-crystalline materials Enthalpic recovery at the glass transition
Heat-Cool-Heat of PET
1.5
1.0
Cool
0.5
0.0
-0.5
-1.0
-1.5
20
60
100
140
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260
Temperature (C)