DSC/MDSC Training Service Meeting Jan 2004 Section 2.

Agenda

Terminology Understanding DSC Understanding MDSC Experimental Parameters Applications

Agenda

Terminology Understanding DSC Understanding MDSC Experimental Parameters Applications

DSC Terminology
Amorphous Phase - The portion of material whose

molecules are randomly oriented in space. Liquids and glassy or rubbery solids. Thermosets and some thermoplastics. Crystalline Phase - The portion of material whose molecules are regularly arranged into well defined structures consisting of repeat units. Very few polymers are 100% crystalline. Semi-crystalline Polymers - Polymers whose solid phases are partially amorphous and partially crystalline. Most common thermoplastics are semi-crystalline. Melting - The endothermic transition upon heating from a crystalline solid to the liquid state. This process is also

DSC Terminology
Crystallization - The exothermic transition upon cooling

from liquid to crystalline solid. Crystallization is a function of time and temperature. Cold Crystallization - The exothermic transition upon heating from the amorphous rubbery state to the crystalline state. This only occurs in semi-crystalline polymers that have been quenched (very rapidly cooled from the melt) into a highly amorphous state. Enthalpy of Melting/Crystallization - The heat energy required for melting or released upon crystallization. This is calculated by integrating the area of the DSC peak on a time basis.

Agenda

Terminology Understanding DSC Understanding MDSC Experimental Parameters Applications

DSC: Typical DSC Transitions

Heat Flow -> exothermic

Oxidation or Decomposition

Melting Glass Transition Crystallization Cross-Linking (Cure)

Composite graph
Temperature

DSC Signals
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 Heat Flow Endothermic: heat flows into the sample as a result of either heat capacity (heating) or some endothermic process (Tg, melting, evaporation, etc.) Exothermic: heat flows out of the sample as a result of either heat capacity (cooling) or some exothermic process (crystallization, cure, oxidation, etc.)

Understanding DSC Signals

Heat Flow Relative Heat Flow: measured by all DSCs except the Q1000. The absolute value of the signal is not relevant, only absolute changes are used. Absolute Heat Flow: used by the Q1000. Dividing the signal by the measured heating rate converts the heat flow signal into a heat capacity signal

Understanding DSC Signals (cont.)

Heat Flow (cont.)

dH dT CP f (T, t) dt dt
Where:
dH dt = measured heat flow rate

Cp = sample heat capacity = specific heat (J/gC) x mass (g)

dT dt = measured heating rate

f (T,t) = heat flow due to kinetic processes (evaporation, crystallization, etc.)

Understanding DSC Signals (cont.)

Heat Flow Due to Heat Capacity Heat Capacity = Specific Heat (J/gC) x mass (g) For a given sample, the higher the heating rate, the higher the heat flow rate. Therefore, high heating rates increase sensitivity to detect weak transitions Heat Flow Rate = mWatt = mJ/sec

The heat flow rate becomes endothermic as heating of the

sample begins (due to sample Cp at that temperature) and becomes more endothermic at higher temperature due to increasing sample Cp at higher temperature During cooling, the heat flow signal is exothermic

dH dT CP f (T, t) dt dt

Heat Flow Due to Heat Capacity

Heating & Cooling

Understanding DSC Signals (cont.)

Heat Flow Due to Heat Capacity (cont.) Absolute Heat Capacity or Specific Heat (J/gC) is important because: 1. It is required by engineers to develop systems that heat or cool materials 2. It is a measure of molecular mobility Vibration occurs below and above Tg Rotation polymer backbone and sidechains (in and above Tg) Translation polymer molecule (above Tg) Changes in heat capacity are important because they signal significant changes in the physical properties of a material

Changes in Cp & Heat Flow

Sample: Polystyrene Size: 14.0200 mg Method: Anneal80 Comment: MDSC.3/40@2; After Anneal @ 80C various times

DSC

File: C:\TA\Data\Len\FictiveTg\PSanneal80.002

-0.3

2.0

-0.4

-0.5

1.5

Heat Capacity

Glass Transition is Detectable by DSC Because of a Step-Change in Heat Capacity

-0.6

Heat Flow Temperature Below Tg - lower Cp - lower Volume - lower CTE - higher stiffness - higher viscosity - more brittle - lower enthalpy

-0.7

1.0

-0.8

-0.9

0.5 70
Exo Up

-1.0 90 110

Temperature (C)

Universal V3.8A TA Instruments

[ ] Heat Flow (mW)

Heat Capacity (J/g/C)

Understanding DSC Signals (cont.)

Heat Flow Due to Transitions Ideally, all transitions in a material are separated by a region of the baseline that is due to just heat capacity In practice, most materials have several transitions that overlap. To improve resolution between transitions: 1. Use lower heating or cooling rates to sharpen transitions 2. Use hermetic vs. crimped pans for samples with volatile components 3. Use higher heating rates to minimize crystal perfection or polymorphic changes 4. Use MDSC to separate kinetic processes from Tg or melting

Cp Baseline
Sample: PET;Iso Cryst@215C Size: 16.0000 mg Method: Heat@20 Comment: Heat@20 after 1 hour @ 215C

DSC

File: C:...\Len\Crystallinity\PETcycle20.005

0
20C/min Heat after Isothermal Crystallization at 215C

0 250
215.00C

-2

-4 -10

Heat Flow (mW)

-6 150 -8 100 -10 50 -12

Cp Baseline

-20
Tg

Cp Baseline

-30
Sample Crystallized at 215C Cp Baseline

-24.99C

-14

-40 85
Exo Up

90

95

100

105

-16 110
Universal V3.8A TA Instruments

Time (min)

[ ] Heat Flow (mW)

Melting

[ ] Temperature (C)

200

Understanding DSC Signals (cont.)

Temperature (Heating Rate) Since the heat flow signal is a function of heating rate, it will be stable only when the heating rate is stable
dH dT CP f (T, t) dt dt

Use the time-based derivative of temperature to

help with interpretation of the heat flow signal MDSC makes deliberate changes in heating rate in order to measure heat capacity

Heating Rate During Indium Melt

Stabilization of Heating Rate

Sample: PET;Iso Cryst@215C Size: 16.0000 mg Method: Heat@20 Comment: Heat@20 after 1 hour @ 215C -4

DSC

File: C:...\Len\Crystallinity\PETcycle20.005

20.5

-6

20.0

Endothermic Glass Transition

-8

19.5 -10
Do Not Attempt to Interpret Transitions Before Heating or Cooling Rate Have Stabilized

-12 -50
Exo Up

50

100

150

19.0 200
Universal V3.8A TA Instruments

Temperature (C)

[ ] Deriv. Temperature (C/min)

An Endothermic Transition Will Absorb Heat and Reduce Sample Heating Rate

Heat Flow (mW)

Agenda

Terminology Understanding DSC Understanding MDSC Experimental Parameters Applications

MDSC Separates Heat Flow

dH dT Cp f (T, t) dt dt

Where:
dH DSC heat flow signal; Watts J/s dt
Cp Sample Heat Capacity; J/ C Sample Specific Heat (J/g C) x Sample Weight (g)

dT Heating Rate; C/min dt

f (T, t) Heat flow that is function of time at an absolute temperatu re (kinetic); J/s

What Does MDSC Measure?

As will be shown, MDSC separates the Total heat flow of
DSC into two parts based on the heat flow that does and does not respond to a changing heating rate MDSC applies a changing heating rate on top of a linear heating rate in order measure the heat flow that responds to the changing heating rate In general, only heat capacity and melting respond to the changing heating rate. Although heat capacity is a reversible thermodynamic property, the change in heat capacity during a transition is almost never reversible The Reversing and Nonreversing signals of MDSC should never be interpreted as the measurement of reversible and nonreversible properties

Sample: Epoxy Size: 9.7900 mg Method: MDSC.5/40@0.5 Comment: MDSC.5/40@0.5C/min 2.0

The Change in Heat Capacity During the Cure of a DSC Reversible Thermosetting Resin Is Not
Sample: Epoxy Size: 9.79 mg Method: MDSC at 5C/min
1.5
Decrease in Cp Due to Crosslinking (Vitrification) Reversing Heat Capacity

File: C:\TA\Data\Len\Epoxy\MDSCcure.001

1.8

1.6

Heat Flow (mW)

1.0

Increase in Cp Due to Linear Polymerization

Increase in Cp Due to Devitrification

1.4

0.5

Total Heat Flow

1.2 0.0

103.62C 319.8J/g

-0.5 50
Exo Up

100

150

1.0 200
Universal V3.8A TA Instruments

Temperature (C)

[ ] Rev Cp (J/g/C)

MDSC Separation of Transitions

MDSC Data Signals
dH dt
Total

dT Cp dt

f (T, t)
Nonreversing

Reversing +

Transitions:

Heat Capacity Enthalpic Recovery Glass Transition Evaporation Most Melting Crystallization Thermoset Cure Protein Denaturation Starch Gelatinization Decomposition Some Melting

Understanding the Heat Flow Signal

For a given sample, the rate of heat flow (mW = J/sec) due to
heat capacity is linearly proportional to heating rate;.

At a heating rate of zero, the heat flow due to heat capacity is

also zero.

dH dT Cp f (T, t) dt dt

Any heat flow detected at a zero heating rate must be due to

kinetic processes (T,t) in the sample

The purpose of MDSC is to separate the total heat flow into

the part that responds to heating rate and the part that responds to absolute temperature

Transitions often have a heat capacity and kinetic (time-dependent) component

2nd Heatobserving how kinetic processes affect the measured heat flow signal

1st Heatobserving how kinetic processes affect the measured heat flow signal

MDSC Nonreversing signal shows timedependent (kinetic) component of transition

Comparison of DSC and MDSC Heat Flow and Heat Capacity Signals
dH dT Cp f (T, t) dt dt
DSC
Total Heat Flow

MDSC
Modulated Heat Flow Total Heat Flow Reversing Heat Flow Nonreversing Heat Flow

COMMENTS
Signals contain all thermal events occurring in the sample Quantitatively the same in both techniques at the same average heating rate Heat capacity component of total heat flow Kinetic component of total heat flow

Heat Capacity All calculated heat flow signals are also available in heat capacity units

Calculation of MDSC Signals

All MDSC signals are calculated from three measured signals. The difference between the calculations for the Q-Series and 2900-Series instruments is that the Q-Series calculates both a sample and reference signal before subtracting them vs. a single differential signal for 2900 instruments Time

Modulated Temperature (Heating Rate) Modulated Heat Flow

Average & Modulated Temperature

62 62

Modulate +/- 0.42 C every 40 seconds (Heat-Iso) Ramp 4.00 C/min to 290.00 C
57.0 57.0

Modulated Temperature
60
Modulated Temperature (C)

60

56.5

Amplitude

56.5

Temperature (C)

56.0

56.0

55.5

55.5

Temperature (C)

58
55.0 55.0

58

54.5 13.70

13.75

13.80

13.85

13.90

13.95

14.00

54.5 14.05

Time (min)

56

56

Average Temperature
54 54

Note that temperature is not decreasing during Modulation i.e. no cooling

52 13.0 13.5 14.0 14.5 52 15.0

Time (min)

Modulated Temperature (C)

Average & Modulated Heating Rate

10 10

Period
8

Note That Heating Rate is Never Negative (no cooling)

Average Heating Rate

Modulated Heating Rate

0 13.0

13.5

14.0

14.5

0 15.0

Time (min)

Deriv. Modulated Temperature (C/min)

Deriv. Temperature (C/min)

MDSC Raw Data SignalsModulated Heat Flow and Modulated Temperature (Heating Rate)

Signal Calculations (cont.)

Total Heat Flow

Equivalent to standard DSC at the same average heating rate Calculated from the average value of the Modulated Heat

Flow The average and amplitude values of the Modulated Heat Flow are calculated continuously (every 0.1 seconds) using Fourier Transform analysis. This provides much better resolution than would be obtained from using the actual 2 average and amplitude values that occur over each modulation cycle

Signal Calculations (cont.)

Reversing Heat Flow Calculated from Reversing Heat Capacity signal
Heat Flow Amp Rev Cp x KCp Rev Heating Rate Amp

Rev Heat Flow Rev Cp x Avg Heat Rate

Signal Calculations (cont.)

Nonreversing Heat Flow

Calculated by subtracting the Reversing Heat Flow

signal from the Total Heat Flow signal
dH dT Cp f (T, t) dt dt

Total = Reversing + Nonreversing Nonreversing = Total Reversing

Calculated MDSC Heat Flow Signals

Agenda

Terminology Understanding DSC Understanding MDSC Experimental Parameters Applications

DSC General Method Recommendations

Determine decomposition temp
Stay below that temperature Run Heat-Cool-Heat @ 10C/min Use specific segments as needed, i.e. gas switch, abort, MDSC, etc. Modify heating rate based on what youre looking for

DSC Experimental Parameters

"Always" do TGA experiments before beginning DSC tests on new materials Heat approximately 10mg sample at 10C/min to determine: a) Volatile content Unbound water or solvent is usually lost over a broader temperature range and a lower temperature than a hydrate/solvate b) Decomposition temperature DSC results are of little value once the sample has lost 3-5% weight due to decomposition (not desolvation) Decomposition is a kinetic process (time + temperature dependent). The measured decomposition temperature will shift to lower temperatures at lower heat rates

DSC Experimental Parameters

Use TGA data to help select DSC experimental
conditions a) Crimped vs. Hermetic (sealed) Pan Use hermetic pan if sample loses approximately 0.5% or more b) Maximum Temperature Excessive decomposition will contaminate DSC cell between runs c) When comparing samples, always use the same experimental conditions

DSC Sample Weight

Selection of the optimum weight is dependent on a number of factors 1. the sample to be analyzed must be representative of the total sample 2. the change in heat flow due to the transition of interest should be in the range of 0.1 - 10mW (Fig 7) - metal or chemical melting; <5mg - polymer Tg or melting; 10mg - composites or blends; >10mg 3. the accuracy of the analytical balance - sample weight should be accurate to 1%

Heat Flow Change During a Transition

DSC Sample Pan

Sample Pan: Crimped vs. Hermetically Sealed
Crimped pans are lighter ( 23mg) and provide better sensitivity and resolution Hermetic aluminum pans are heavier ( 55mg) but can be sealed to prevent loss of volatiles Hermetic stainless steel pans ( 250mg) permit use of large samples (100mg) and higher temperatures/pressures (2000 psig = 1.4 MPa) Care should be taken to keep the bottom of all pans flat to improve heat transfer/resolution

DSC Experimental Parameters

Experimental Conditions (cont.)

Select an end-temperature which does not cause decomposition of the sample to occur in the DSC. Decomposition products can condense in the cell and cause either corrosion of the cell or baseline problems Use sealed glass ampoules or stainless steel pans, which can take high pressure (>1000psi), in order to study decomposition by DSC

MDSC Experimental Parameters

MDSC controls the Heating Rate(s) applied to the sample through three experimental parameters:

1. Average Heating Rate (C/min) Typically less than 5C/minute in order to get a minimum of 4-5 temperature modulations during a transition
2. Temperature Modulation Amplitude ( C) Typically 0.1 to 2C 3. Temperature Modulation Period (Seconds) Typically 40 100 seconds

Calibration of MDSC Cp Constant

When measuring transitions in materials by MDSC, it is not necessary to perform heat capacity calibration as long as: 1. The modulation period is long enough for the sample to follow the temperature modulation (Figure 17) Crimped pans with samples up to 15 mg 40 sec. Q Series, 60 sec. 2920 Hermetic pans with samples up to 10 mg 60 sec. Q Series, 80 sec 2920 For measuring absolute values of heat capacity, use 100 seconds for crimped pans and 120 seconds for hermetic pans. It is best to calibrate for heat capacity when measuring absolute values. Note; Set the Reversing Heat Capacity Calibration Constant to a value of 1.0 for the for the Q-Series and 1.1 for the 2920 if no calibration constant is measured

Calibration of MDSC Cp Constant

No additional calibration is required as long as:

2. The modulation amplitude falls in the range

between 0.1 and 2.0C Values < 0.1C result in decreased sensitivity Values > 2.0C result in decreased resolution

MDSC Experimental Parameters

Sample Preparation

Use flat, thin samples if possible Sample Limitations It is not possible to make reliable measurements of Heat Capacity or any other MDSC signal (except Total) if it is not possible to modulate the temperature of a sample during a transition. Very large samples (20 50 mg) can be used to measure very weak transitions. The only limitation is that the absolute value of the measured heat capacity will be low.

MDSC Experimental Parameters

Measurement of Heat Capacity Purpose is to measure heat capacity in temperature regions where there are no transitions Optimum Conditions Heating Rate; isothermal up to 5C/min Modulation Period 100 seconds with crimped pans 120 seconds with hermetic pans Modulation Amplitude; 1.5X Table Value with a minimum of 0.5C Sample Size; 10-15mg

MDSC Experimental Parameters

Glass Transitions (Tg) For standard Tg: Sample Size: 10 15 mg Period: 40 seconds Amplitude 2X Table Heating Rate: 3C/min

Tg is Hard to Detect (Figures 19 21) Sample Size: 10 20 mg Amplitude: 4X Table Period: 60 seconds Heating Rate: 2C/min Tg has Large Enthalpic Relaxation Sample Size: 5 10 mg Amplitude: 1.5X Table Period: 40 seconds Heating Rate: 1C/min Note; These are reasonable starting conditions which may need to be adjusted depending on the transition of interest

MDSC Experimental Parameters

Optimum conditions for analysis of sample melting and crystallinity: Sample Size; 10-15mg Period 40 sec. Q Series, 60 sec 2900 for crimped pans 60 sec. Q Series, 80 sec 2900 for hermetic pans Heating Rate Slow enough to get a minimum of 4-5 cycles at half-height of the melting peaks Amplitude Use Heat-Iso amplitude which provides no cooling during temperature modulation (see Table). The benefit of this will be illustrated later

MDSC Heat-Iso Amplitudes (no cooling)

P e r i o d ( s e c )

4 0 5 0 6 0 7 0 8 0 9 01 0 0
H e a t i n g R a t e

0 . 0 1 1 0 . 0 1 3 0 . 0 1 6 0 . 0 1 9 0 . 0 2 1 0 . 0 2 4 0 . 0 2 7 0 . 1 0 . 2 0 . 0 2 1 0 . 0 2 7 0 . 0 3 2 0 . 0 3 7 0 . 0 4 2 0 . 0 4 8 0 . 0 5 3 0 . 0 5 3 0 . 0 6 6 0 . 0 8 0 0 . 0 9 3 0 . 1 0 6 0 . 1 1 9 0 . 1 3 3 0 . 5 1 . 0 0 . 1 0 6 0 . 1 3 3 0 . 1 5 9 0 . 1 8 6 0 . 2 1 2 0 . 2 3 9 0 . 2 6 5 2 . 0 0 . 2 1 2 0 . 2 6 5 0 . 3 1 8 0 . 3 7 1 0 . 4 2 4 0 . 4 7 7 0 . 5 3 1 5 . 0 0 . 5 3 1 0 . 6 6 3 0 . 7 9 6 0 . 9 2 8 1 . 0 6 1 1 . 1 9 4 1 . 3 2 6
T h i s t a b l e i s a d d i t i v e , i . e . t h e h e a t o n l y a m p l i t u d e f o r a p e r i o d o f 4 0 s e c a n d h e a t i n g r a t e o f 2 . 5 C / m i n . i s t h e s u m o f t h e v a l u e s f o r 2 . 0 C / m i n a n d 0 . 5 C / m i n : A m p l i t u d e ( 4 0 s , 2 . 5 C / m i n ) = 0 . 2 1 2 + 0 . 0 5 3 = 0 . 2 6 5 C

Agenda

Terminology Understanding DSC Understanding MDSC Experimental Parameters Applications

Applications Agenda
Heat Capacity Glass Transitions Melting & Crystallization

Applications Agenda
Heat Capacity Glass Transitions Melting & Crystallization

Specific Heat Capacity

Heat capacity is the amount of heat required to
raise the temperature of a material from T1 to T2

True Heat Capacity (no transition) is completely

reversible; the material releases the same amount of heat as temperature is lowered from T2 to T1

Specific Heat Capacity refers to a specific mass

and temperature change for a material (J/gC)

Importance of Heat Capacity

Thermodynamic property of material(vs. heat

flow)
Measure of molecular mobility Provides useful information about physical

properties of the material as a function of temperature

Benefit of Using Heat Capacity Signal

Benefits of using a heat capacity (instead of heat
flow) signal include: The ability to overlay signals from samples run at different heating rates (See examples) The ability to overlay signals from heating and cooling experiments (see examples)

Heat Flow of PET w/ Different Heating Rates

Cp of PET w/ Different Heating Rates

Heating & Cooling Experiment

Tg on Heating & Cooling

Calculating Heat Capacity (Cp)

Depending on the DSC that you have there are
three different ways to calculate Cp 1) Three Run Method ASTM E1269 Applicable to all DSCs 2) Direct Cp Single Run Method Applicable to Q1000 only 3) MDSC - Single Run Method Any TA Instruments DSC w/ MDSC option Most accurate determination

Three Run Method Generally, three experiments are run over a

specific temperature range Allow 5 minute isothermal at start Use 20C/min heating rate Empty pan run Match pan/lid weights to 0.05 mg Used to establish a reference baseline Sapphire run Used to determine calibration constant Use same weight of pan/lid as above 0.05 mg Typical weight is 20 25 mg Sample run Typical weight is 10 15 mg Use same weight of pan/lid as above 0.05 mg

Three Run Method

How is Heat Capacity Measured? (cont.) Older instruments calculate the samples specific heat capacity using the following equation

Where: Cp = K = H = 60 = Hr = M =

K x H x 60 Cp Hr x M
specific heat capacity (J/gC) calibration constant from sapphire run difference in heat flow between empty pan run and either sapphire or sample run at a specific temperature (Figure 19) conversion from min to sec heat rate (C/min) sample mass (mg)

Cp by Traditional DSC 3 Runs

Heat Flow
5 400

Baseline Run
0 300 -5

Sample Run
Temperature (C)

Heat Flow (mW)

200 -10

Calibration Run
-15 100

-20 0 -25

-30 0 10 20 30 40

-100

Time (min)

Cp by Traditional DSC 3 Runs

6 500

Cp & Total Heat for PET

280.00 C 454.6 J/g

400

Heat Capacity (J/g/C)

150.00 C 174.6 J/g

200 2

50.00 C 1.161 J/g/C 150.00 C 1.609 J/g/C 50.00 C 34.94 J/g

0 0 50 100 150 200 250

280.00 C 1.924 J/g/C

100

0 300

Temperature (C)

Total Heat (J/g)

300

Direct Cp Q1000 Only

The Q1000 has the ability to calculate a heat
capacity signal directly from a single run
Heat Flow Cp xK Heating Rate

Where K is a calibration factor

Direct Cp of Quenched PET

Sample: PET; Quenched Size: 16.0000 mg Method: Heat@20 Comment: Heat@20 6

DSC

File: C:...\Crystallinity\RIqPETcycle20.001

600

275.00C 530.8J/g

Heat Capacity (Single Run) 135.54C 0.7311J/g

200
Running Integral

-2 0 50 100 150 200 250

0 300
Universal V3.8A TA Instruments

Temperature (C)

[ ] Integral (J/g)

Heat Capacity (J/g/C)

400

Cp by MDSC
With MSDC Cp can also be plotted out directly

Plot Rev Cp to plot heat capacity

With Q series, Cp signals are also available for Total
& Non-Rev (These are Heat Flow signals normalized by the heating rate)

Cp by MDSC
8

600

Integral (J/g) {Total Heat}

Use Running Integral to Calculate Total Heat

Rev Cp (J/g/C)

400

200

0 50 100 150 200 250 300

Temperature (C)

What Affects the Heat Capacity?

Amorphous Content Aging Side Chains Polymer Backbone Copolymer Composition

Anything that effects the mobility of the molecules, affects the Heat Capacity

Effect of Amorphous Content on Cp

Amorphous Cp is greater than Crystalline Cp
Amorphous Content increases Specific Heat Capacity

Crystalline polymers contain more order and thus fewer degrees of molecular motion. Less molecular motion results in lower specific heat capacity.

Applications Agenda
Heat Capacity Glass Transitions Melting & Crystallization

The Glass Transition

The Glass Transition is the reversible change of the

amorphous region of a polymer from, or to, a viscous or rubbery condition to, or from, a hard and relatively brittle one
The Glass Transition Temperature is a temperature

taken to represent the temperature range over which the glass transition takes place
Detected by DSC as an increase in Cp

Measurement of Tg
-0.15

Start
-0.20

Extrapolated Onset
53.49C

88.27C

Midpoint & Change

93.01C(H) 0.04705W/g

Heat Flow (W/g)

-0.25

-0.30

98.33C 125.49C

Extrapolated End
-0.35 20
Exo Up

End
100 120 140 160

40

60

80

Temperature (C)

Measurement of Tg
-0.15

-0.20

Heat Flow (W/g)

-0.25

93.01C(H)

-0.30

-0.35 20
Exo Up

40

60

80

100

120

140

160

Temperature (C)

Tg is Reversible

Some Properties Affected at Tg

Physical property
Specific Volume Modulus Coefficient of thermal expansion Specific Heat Enthalpy Entropy

Response on heating through Tg Increases V, 1/E, Decreases Increases Increases Increases Increases

Tg

CTE

Cp H& Temperature S

What Affects the Glass Transition?

Heating Rate Heating & Cooling Aging Molecular Weight Plasticizer Filler Crystalline Content Copolymers Side Chains Polymer Backbone Hydrogen Bonding

Anything that effects the mobility of the molecules, affects the Heat Capacity, which in turn affects the Tg

Effect of Heating Rate on the Tg

Effect of Cooling Rate on Tg

2 . 0

H e a t C a p a c i t y M e a s u r e d A f t e r C o o l i n g a t Q u e n c h , 2 0 , 1 0 , 5 , 2 , 1 a n d 0 . 2 C / m i n 1 . 8 Q u e n c h

1 . 6 1 . 4

increased amorphous fraction

2 0 1 0 0 . 2

HeatCpacity(J/gC)

1 . 2 1 . 0 2 04 06 08 01 0 01 2 01 4 01 6 0 T e m p e r a t u r e ( C )

Optimizing Measurement of Tg
If Tg is hard to see: Use larger sample weight

Use higher heating rate

Use MDSC

Applications Agenda
Heat Capacity Glass Transitions Melting & Crystallization

Melting and Crystallization

Melting is the endothermic transition from a
crystalline solid to a liquid amorphous state Crystallization is the exothermic transition from amorphous to crystalline (normally from liquid to solid during cooling) Cold-Crystallization is the exothermic transition during heating from a solid amorphous state to a solid crystalline state.

Measurement of Melting
0.0 -0.2

Extrapolated Onset & Integrated Area

242.65C -77.27J/g

-0.4

221.83C

271.52C

Heat Flow (W/g)

-0.6

Start
12.28C

End

-0.8

Width @ Half height

-1.0

-1.2

256.26C -0.8930W/g
-1.4 160
Exo Up

Peak & Height

300 320 340

180

200

220

240

260

280

Temperature (C)

Measurement of Melting
0.0 -0.2

242.65C -77.27J/g

-0.4

Heat Flow (W/g)

-0.6

-0.8

-1.0

-1.2

256.26C

-1.4 160
Exo Up

180

200

220

240

260

280

300

320

340

Temperature (C)

DSC Melting
Polymers
The peak temperature is the melt point Between the extrapolated onset and the peak, crystal perfection may be occurring Between the peak and the end the sample is finished melting and returning to the DSC temperature

Pure, low molecular weight materials

(mw<500g/mol) (small molecules)
The extrapolated onset is the melting temperature All of the crystals are melted at the peak Between the peak and the end the sample is finished melting and returning to the DSC temperature

Calculation of % Crystallinity
Sample must be pure material, not copolymer or filled Must know enthalpy of melting for 100% crystalline material (DHlit)
For standard samples: % crystallinity = 100* DHm / DHlit

For samples with cold crystallization:

% crystallinity = 100* (DHm - DHc)/ DHlit

How Crystalline is this Sample?

1.0

Quenched Cooled PET

134.60C

0.5

Heat Flow (W/g)

0.0

242.92C -74.70J/g
-0.5

127.71C 54.14J/g

-1.0

Size: 9.5600 mg Method: 10C/mint 256.26C

-1.5 0
Exo Up

50

100

150

200

250

300

Temperature (C)

First Heat @ 10C/min

0.0

Heat Flow (W/g)

-0.5

-1.0

0
Exo Up

50

100

150

200

250

300

Temperature (C)

Add Cool @ 10C/min

1.0

0.5

Heat Flow (W/g)

0.0

-0.5

-1.0 0
Exo Up

50

100

150

200

250

300

Temperature (C)

Add Second Heat @ 10C/min

1.0

0.5

Heat Flow (W/g)

0.0

-0.5

-1.0 0
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Temperature (C)

Zoom in on Tg
1.0

0.5

Heat Flow (W/g)

0.0

-0.5

-1.0 0
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Temperature (C)

Observation of Crystallization
Crystallization is a two step process: Nucleation Growth The extrapolated onset is the nucleation temperature The peak maximum is the crystallization temperature

Observation of Crystallization
1.0

Peak
0.9

160.65C

0.8

Heat Flow (W/g)

0.7

183.75C 14.68J/g

0.6

0.5

Extrapolated Onset & Integrated Area

0.4 0
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Temperature (C)

Effect of Nucleating Agents

2.0

crystallization
1.5

POLYPROPYLENE WITHOUT NUCLEATING AGENTS

POLYPROPYLENE WITH NUCLEATING AGENTS

Heat Flow (W/g)

0.0

1.0
Heat Flow (W/g)
-0.5

-1.0

melting
0.5
-1.5 60
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Temperature (C)

0.0 40
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Temperature (C)