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DSC: Differential Scanning Calorimetry

A bulk analytical technique

What Does a DSC Measure?


A DSC measures the difference in heat flow rate (mW = mJ/sec) between a sample and inert reference as a function of time and temperature

Endothermic Heat Flow


0 .1

Heat Flow
0 .0 -0 .1

Heat Flow (W/g)

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 )

Exothermic Heat Flow

0 .1

Heat Flow (W/g)

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

Base Surface Constantan Wire Chromel Wire Chromel Wire

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

Understanding DSC Signals


Heat Flow Relative Heat Flow: measured by many DSCs. The absolute value of the signal is not relevant, only absolute changes are used.

Absolute Heat Flow: used by TAs Q1000.


Dividing the signal by the measured heating rate converts the heat flow signal into a heat capacity signal

DSC Heat Flow


dH = DSC heat flow signal dt
Cp = Sample Heat Capacity = Sample Specific Heat x Sample Weight

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)

Tzero Heat Flow Equation


Heat Flow Sensor Model
qs Cs Ts Rs Cr Tr Rr qr

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

Measuring the Cs & Rs


Tzero Calibration calculates the Cs & Rs Calibration is a misnomer, THIS IS NOT A
CALIBRATION, but rather a measurement of the Capacitance (C) and Resistance (R) of each DSC cell After determination of these values, they can be used in the Four Term Heat Flow Equation showed previously

Measuring the Cs & Rs


Preformed using Tzero Calibration Wizard
1. Run Empty Cell 2. Run Sapphire on both Sample & Reference side

Measuring the Cs & Rs


Empty DSC constant heating rate Assume:
qs = qr 0

Heat balance equations give sensor time constants


T0 s = Cs Rs = dTs d
T0 T r = Cr Rr = dTs dT d d

Measuring the Cs & Rs


Repeat first experiment with sapphire disks on sample and reference (no pans) dTs dTr Assume: qs = ms csapph qr = mr csapph d d Use time constants to calculate heat capacities
ms csapph Cs = T0 1 dTs s d
mr csapph Cr = T0 + T 1 dTs dT r d d

Measuring the Cs & Rs


Use time constants and heat capacities to calculate thermal resistances
Rs =

s
Cs

Rr =

r
Cr

A few words about the Cs and Rs


The curves should be smooth and continuous,
without evidence of noise or artifacts Capacitance values should increase with temperature (with a decreasing slope) Resistance values should decrease with temperature (also with a decreasing slope) It is not unusual for there to be a difference between the two sides, although often they are very close to identical

Good Tzero Calibration Run

Bad Tzero Calibration Run

Can see that it is bad during Tzero cal run

Before Running Tzero Calibration


System should be dry Dry the cell and the cooler heat exchanger
using the cell/cooler conditioning template and the default conditions (2 hrs at 75C) with the cooler off Preferably enable the secondary purge Do not exceed 75C cell temperature with the cooler off, although the time can be extended indefinitely

Stabilization before Calibration


System must be stable before Tzero
Calibration Stabilization is achieved by cycling the baseline over the same temperature range and using the same heating rate as will be used for the subsequent calibration Typical systems will stabilize after 3-4 cycles, 8 cycles recommended to ensure that the system has stabilized

Example of Typical Results


Characteristics of the thermal resistances and heat capacities: 70 Both curves should be smooth, with no steps, spikes or inflection points. Thermal resistances should always have negative slope that gradually decreases. Heat capacities should always have positive slope that gradually decreases.
Reference Capacitance (Joule/C)
60 60 0.04 0.05

0.04

Reference Resistance (C/Watt)

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)

Sample Capacitance (Joule/C)

Sample Resistance (C/Watt)

Tzero vs Conventional Baseline


0.6

Conventional Baseline T zero Baseline

0.4

Heat Flow (mW)

0.2

0.0

-0.2

-0.4 -100

100

200

300

400

Temperature (C)

Indium with Q Series Heat Flow Signals


Q1000

Q100

Q10

Keeping the DSC Cell Clean


One of the first steps to ensuring good data is
to keep the DSC cell clean How do DSC cells get dirty? Decomposing samples during DSC runs Samples spilling out of the pan Transfer from bottom of pan to sensor

How do we keep DSC cells clean?

DO NOT DECOMPOSE SAMPLES IN


THE DSC CELL!!!

Run TGA to determine the decomposition


temperature Stay below that temperature! Make sure bottom of pans stay clean Use lids Use hermetic pans if necessary

TGA Gives Decomposition Temperature

Cleaning Cell
If the cell gets dirty
Clean w/ brush Brush gently both sensors and cell if necessary Be careful with the Tzero thermocouple

Blow out any remaining particles

Brushing the Sample Sensor

It Does Matter What Pan you use

Monohydrate Pharmaceutical sample

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

If powder, spread evenly over the bottom of the


pan

Using Sample Press


When using crimped pans, dont over crimp Bottom of pan should remain flat after crimping
Crimped Pans Hermetic Pans

Good

Bad

Not Sealed Sealed

When using Hermetic pans, a little more


pressure is needed Hermetic pans are sealed by forming a cold wield on the Aluminum pans

Sample Size
Larger samples will increase sensitivity
but. Larger samples will decrease resolution

Goal is to have heat flow of 0.1-10mW going


through a transition

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

Effect of Sample Size on Indium Melt


0

Size: 1.2100 mg
-5

Size: 0.4900 mg

Heat Flow (mW)

-10

Size: 5.7010 mg

-15

-20

-25 150

Weight (mg) 0.49 1.21 5.70


152 154 156 158

Onset (C) 156.41 156.45 156.61


160

Peak (C) 156.56 156.76 157.17


162

Width (C) 0.17 0.29 0.55


164

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

Sample Temperature Range


Rule of Thumb
Have 2-3 minutes of baseline before and after transitions of interest - if possible

DO NOT DECOMPOSE SAMPLES IN DSC CELL


Temperature range can affect choice of pans Just because the instrument has a temperature range of 90C to 550C (with RCS) doesnt mean you need to heat every sample to 550!

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 )

Deriv. Temperature (C/min)

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

Good starting point is 10C/min

Effect of Heating Rate

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

Run Heat-Cool Heat experiments to see effect


of & eliminate thermal history
Heat at 10C/min Cool at 10C/min Heat at 10C/min

Heat-Cool-Heat of PET
1.5

1.0

Cool
0.5

Heat Flow (W/g)

0.0

Second Heat First Heat

-0.5

-1.0

-1.5

20

60

100

140

180

220

260

Temperature (C)

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