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DSC 2000
DSC 2000
Theory and Experimental Conditions Glass Transition Melting and Crystallization Heat Capacity MDSC
Differential Scanning Calorimetry (DSC) measures the temperatures and heat flows associated with transitions in materials as a function of time and temperature in a controlled atmosphere. These measurements provide quantitative and qualitative information about physical and chemical changes that involve endothermic or exothermic processes, or changes in heat capacity.
TA Instruments DSCs
DSC 2010
DSC 2910
DSC 2920
DSC: Definitions
A calorimeter measures the heat into or out of a sample. A differential calorimeter measures the heat of a sample relative to a reference. A differential scanning calorimeter does all of the above and heats the sample with a linear temperature ramp. Endothermic heat flows into the sample. Exothermic heat flows out of the sample.
Sample Temperature Ts
Furnace Temperature
Lid
Chromel Disc
Purge Preheated: for very low noise from turbulence Air Cool: for fast return to room temperature
Heat Flow =
T R
k 1 k 2 where: T = temperature difference (potential) R = thermal resistance of constantan disk k 1 = factory-set calibration value k 2 = user-set calibration value
DSC: How Heat Flux is Measured temperature difference T. The temperature difference is measured as the voltage difference U between the sample and reference constantan/chromel junctions. The voltage is adjusted for thermocouple response S and is proportional to heat flow. T = U / S T in C U in V S in V/C
Heat flow through the chromel wafer causes a
DTA
Differential Thermal Analysis (DTA) : measures the temperatures and temperature differences (between sample and reference) associated with transitions in materials as a function of time and temperature in a controlled atmosphere
PDSC
Pressure DSC (PDSC) : capability of operating at elevated pressure or at a vacuum (TAI PDSC: 1 Pa - 7 Mpa)
SDT 2960
SDT 2960 Simultaneous DSC-TGA: measures heat flow and weight changes simultaneously
Oxidation or Decomposition
Temperature
the baseline should have three (3) minutes to completely stabilize prior to the transition of interest. Therefore, at 10C/min., start at least 30C below the transition onset temperature a three (3) minute baseline after the transition of interest in order to correctly select integration or analysis limits
zEnd Temperature
Allow
Differential Heat Flow (Cell Constant) Temperature Baseline zMiscellaneous Purge Gas Cooling Accessories Environment zSample Preparation zSelecting Experimental Conditions zRoutine Maintenance/Sample Press
Heat Flow (ASTM E968) Heat of fusion (melting) standards Heat capacity (no transition)
zMiscellaneous
Use specific purge gas at specified rate Calibrate w/cooling accessory functioning if it will be used to run samples Single point used for heat of fusion which is typically accurate to +/- 1-2% from -50C to 350C Calibration should not change w/heating rate
-5
Sample: Indium, 5.95 mg. CALIBRATION MODE; 10C/MIN CALIBRATION BASED ON 28.42J/g
-10
Cell Const.: 1.0766 Onset Slope: -20.82 mW/C
metals (indium, lead, etc.) typically used Extrapolated onset is used as melting temperature Sample is fully melted at the peak
z Miscellaneous
With
metal standards, calibration should change very little with heating rate With metal standards, it is not practical to calibrate for changes in heating rate on polymer samples
10
157.09C PEAK
0 162 164
158
160
five points
zUse tin, lead, and zinc one time only
Temperature
z Cyclopentane* -150.77C z Cyclopentane* -135.09C z Cyclopentane* -93.43C z Cyclohexane# -83C z Water# 0C z Gallium# 29.76C z Phenyl Ether# 30C z p-Nitrotoluene( 51.45C z Naphthalene( 80.25C z Indium# 156.60C z Tin# 231.95C
* GEFTA recommended Thermochim. Acta, 219 (1993) 333. # ITS 90 Fixed Point ( Zone refined organic compound (sublimes)
Phone: 44 (0) 181 943 7565 Fax: 44 (0) 181 943 7554 Email: orm@lgc.co.uk
instrument calibration
zISO/GLP certification often requires third party
calibration of instruments: Service provided by TA Instruments service representative using certified materials Certificate of Calibration issued showing traceability of calibration to a national laboratory
-3 -4 -5 154
156
158
166
168
170
Typical weight of polymer sample is 10mg (2 films at 5mg each) with 1-3mg of Indium
DSC
-2
Polyethylene Melt
Indium Melt
-4
-2
-4
-6
-0.5
-1.0
Heating Rates = 2, 5, 10 & 20C/min
-1.5
-2.0 154 156 158 160 162 164 166 168 170 Temperature (C)
DSC: Effect of Heating Rate on Indium Melting When Placed Between Polymer Film Onset Variation When Calibrated at 10C/min.
Heating Rate 2C/min 5 10 20 Standard Sample -0.12C -0.07 0 +0.15 Polymer Sandwich Sample +.03C +.16 +0.44 +0.82
empty pans Polymers should always have an endothermic slope due to increasing heat capacity with increasing temperature zCurvature Not normally part of calibration procedure Can be eliminated if necessary with baseline subtraction Curvature can cause errors in analyses
0.2
-0.1
0.0
Heating @ 3.5C/min
-0.2 -0.2 100 150 200 250 300 Temperature (C) 350
of purge gas and flow rate affect calibration and therefore should be controlled Nitrogen is preferred because it is inert and calibration is least affected by changes in flow rate
zCooling Accessories
If
used, they should be operating and equilibriated prior to calibration or sample runs
zWarm-up Time/Environment
Electronics
should be given at least one hour to stabilize for important samples if the instrument has been turned OFF Electronics are effected by ambient temperature. Avoid areas such as hoods or near an air conditioner
DSC: Recommended Purge Gas Flow Rates & Effect of Flow Rate
Purge Port (mL/min.) Module DSC 2920/2910/2010 Purge 50 (N2 ) 25 (He) Cool Vacuum 50* 50
* Only needed for subambient or MDSC use. Use dry nitrogen or He gas
Purge Gas Flow Rate Too Slow: Moisture Accumulation and Early Aging of the Cell
Purge
Cell Constant
1.50 1.40 1.30 1.20 1.10 1.00 0 10 20 30 40 50 60 70 80 90 100 110 Nitrogen Cell Constant
of the optimum weight is dependent on a number of factors. The sample to be analyzed must be representative of the total sample The change in heat flow due to the transition of interest should be in the range of 0.1 - 10mW - metal or chemical melting: <5mg - polymer Tg or melting: 10mg - composites or blends: >10mg The accuracy of the analytical balance - sample weight should be accurate to +1%
143.70C 34.95J/g
60
80
180
200
220
sample as thin as possible and cover as much of the pan bottom as possible Samples should be cut rather than crushed to obtain a thin sample Lids should be used with sample pans in order to keep the sample in contact with the bottom of the pan
zSample Pans
Use
lightest, flattest pan possible Use hermetic pans to prevent evaporation if it occurs in the same temperature range as the transition of interest
sample
Never
use a material in the reference pan that has a transition in the temperature range of interest
Because
DSC measures the difference in heat flow between a sample and reference, the baseline stabilizes faster if the difference in heat capacity between the sample and reference is kept small by adding weight (same material as pan) to the reference pan so that it is similar in total weight to the sample pan.
REFERENCE PAN WITH 2 LIDS 1.688mW REFERENCE PAN WITH 1.5 LIDS -0.6018mW -1.953mW REFERENCE PAN WITH LID Sample: Epoxy Weight: Approx. 10mg Heat Rate: 20C -10.04mW NO REFERENCE PAN
170
DSC: Comparison of DSC Tg Using No Reference Pan and One of Equal Cp to Sample
-0.6 -0.8 90
110
130
150
170
dQ dt
heat flow measured by DSC
Low
=
=
Cp
heat capacity or weight of sample
x
x
dT dt
heating rate
+
+
f (T, t)
time dependent or kinetic component
zPurge Gas
nitrogen
increases sensitivity because it is a relatively poor thermal conductor helium increases resolution because it is a good conductor of heat to or from the sample
(in N2)
Hermetic Al Alodined Hermetic Gold Hermetic High Volume (100L) Al Solid Fat Index (SFI) Platinum
(in N2) 600C (3 atm.) 600C (3 atm.) 725C (6 atm.) 250C (safety lid) 600C (no cover) 725C (no cover)
Pan Type std., hermetic, open SFI, open std. hermetic hermetic, SFI, open hermetic SFI, open alodined or gold hermetic high volume
purge = 50mL/min. Ramp 20C/min. to 600C Isothermal for 10 min. Cool cell to room temperature Brush out cell with fiberglass brush Check for improved baseline performance
zNEVER use solvents to clean DSC cell
Tg < Tm
Crystallizable polymer can crystallize on cooling from the melt at Tc
heat data is a function of the material and an unknown thermal history segment data provides information on the crystallization properties of the polymer and gives the sample a known thermal history heat data is a function of the material with a known thermal history
Cooling
Second
Cool
223.01C 48.03J/g
First Heat
-0.2 -0.4 -0.6 -0.8 20 40 60 80 100 120 140 160 180 200 220 240 260 280 Temperature (C)
the materials are different then there will be differences in the Cool and Second Heat results If the materials are the same and they have had the same thermal history then all three (H-C-H) segments will be similar If the materials are the same but they have had different thermal histories then the Cool and Second Heat segments are similar but the First Heats are different
Selecting Experimental Conditions During first heat the maximum temperature must be higher than the melting peak end; eventually an isothermal period must be introduced too high temperature/time: decomposition could occur too low temperature/time: possibly subsequent memory effect because of the fact that crystalline order is not completely destroyed For non-crystallizable (amorphous) thermoplastics the maximum temperature should be slightly above Tg (removal of relaxation effects, avoid decomposition)
Thermosetting Polymers
A+B C Thermosetting polymers react (cross-link) irreversibly. A+B will give out heat (exothermic) when they crosslink (cure). After cooling and reheating C will have only a glass transition Tg.
GLUE
-0.1
aged
0.2
Tg
Residual Cure
102.64C 20.38J/g
Tg
1.5
DSC Conditions: Heating Rate = 10C/min. Temperature Range = -50C to 250C N2 Purge = 50mL/min. 145.4J/g 54.55 % cured Under-cured Sample
1.0
-12.61C(H)
0.5
-5.27C(H)
0.0
Optimally-cured Sample
zWhat is it? zHow is it observed and measured? zWhat affects 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.
Tg
To
Tf Tm
1/2h
HEAT FLOW
1/2h
Ti
Te
Tr
endo
TEMPERATURE (C)
-0.7
-0.8
0. 3005m W
-0.9
79. 88 C
Heating Rate Heating & Cooling Aging Molecular Weight Plasticizer Filler
Sensitivity
poor good very good
Reproducibility
very good good poor
10 C/min COOLING
20 10 0.2
DSC: Effect of Aging on the Glass Transition [M. Todoki, Polymer Data Handbook]
Cold Crystallization Glass Transition As-Spun 2 days 28 days 196 days 3 years and 2 months 4 years and 11 months
50
100
150
DSC
Lab 3-Jun-97
16:41
0.2
0.0
-0.1
-0.2
Heat Fl ow ( W / g)
zDecreases magnitude of Cp shift zBroadens temperature range of Glass Transition zIncreases the Tg
DSC: Copolymers
490
PPO (wt. %)
Side Chain -H
-C6H4 - (4 - C6H5 )
Tg (C) 59 56 93 159
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. zCrystalline Phase - The portion of material whose molecules are regularly arranged into well defined structures consisting of repeat units. Very few polymers are 100% crystalline. zSemi-crystalline Polymers - Polymers whose solid phases are partially amorphous and partially crystalline. Most common thermoplastics are semi-crystalline. zEndothermic - A transition which absorbs energy. zExothermic - A transition which releases energy. zMelting - The endothermic transition upon heating from a crystalline solid to the liquid state. This process is also called fusion. The melt is another term for the polymer liquid phase. zCrystallization - The exothermic transition upon cooling from liquid to crystalline solid. Crystallization is a function of time and temperature. zCold 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. zEnthalpy 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.
z
Observation of Melting
0.0
Extrapolated Onset Temperature 236.94C 45.30J/g Area under the curve (Heat of Fusion)
-0.2
-0.4
12.73C
-0.6
-0.8
250.61C
-1.0
Peak Temperature
To is the onset to melting Tp is the melting peak temperature Te is the end of melting
Pure, low molecular weight materials (mw<500 g/mol) To is used as the melting temperature (T m) Between To and Tp the sample is melting Between Tp and Te the molten sample is returning to the DSC temperature Polymers Tp is used as the melting temperature (T m) Between To and Tp crystal perfection is occurring (both melting and crystallization occurs simultaneously) Between Tp and Te the sample is finishing melting and returning to the DSC temperature
131.12C 157.85C
12.20C
0.2
0.1
16.10C
22.27(24.02)J/g
0.0 -20
Exo Up
1.754J/g
-10
10
20
30
40
Universal V2.5D TA Instruments
Temperature (C)
0.2
23.04J/g
Tc
Tn
139.47C 36.60J/g
Te
140
160
180
200
Temperature (C)
zThe onset temperature is the nucleation (TN ) zThe peak maximum is the crystallization
temperature (TC )
-0.4
-0.6
249. 75 C
250
material (H lit ) zYou can use a standard H lit for relative crystallinity
For standard samples: % crystallinity = 100* Hm / Hlit For samples with cold crystallization: % crystallinity = 100* (Hm - Hc)/ Hlit
130 110 90
ENDO 0
8 6 TIME (min)
10
12
14
DSC: Applications
zEffect of heating/cooling rate zCrystallization kinetics zEffects of polymer structure/composition zEffects of thermal/mechanical processing
0.2 mW
0.5C/min
HEAT FLOW
endo 1
240 2
32C/min
Heat Flow (mW) 50
16
30
8 4 2 1 0.5
120 130
10
Temperature (C)
Nucleation Crystal growth zNucleation may be Natural Induced (using nucleation agents) zThermally influenced process Natural nucleation Crystal growth Modeled by Isothermal Kinetics using the Autocatalytic Model
OVERSHOOT TEMP)
zHold isothermally zRecord time to crystallization peak (tc)
T2
T3 T4
Blank run
3 Time (min)
NUCLEATED POLYPROPYLENE
Exothermic
NON-NUCLEATED POLYPROPYLENE
200 Heat Flow (mW) 150 100 50 0 -50 -30 -25 -20 -15 -10 -5 0 5 10 Temperature (C)
+ -15.55C
134.5
133.5
133.0 8 10
132.5
Temperature (C)
134.0
-Ph-S-
Tm (C) -10 54 66 75
PEEK
Heat Flow (W/g) -0.1
303.61C
-0.2
-0.3 260
280
300
320
340
360
380
Tm (C)
133
129
1.0
3.0
5.0
7.0
% Aromatic 0 39 62 70
Melting Range 105 - 135C 250 - 275C 300 - 315C 300 - 360C
Melting and crystallization are phase changes from organized solid to amorphous phases and vice-versa. Melting is a one-step process while crystallization involves nucleation and crystal growth. The enthalpy of melting can be used to measure crystallinity or filler.
Any process that makes it easier for molecules to be organized will raise the melting temperature.
DSC: Specific Heat Capacity zWhat is it? zHow is it observed and measured? zMethods for calculating specific heat capacity zWhat affects the specific heat capacity of a
polymer?
temperature of one gram of a particular material one kelvin of temperature. Specific Heat Capacity is due to the molecular motion in a material (units of J/g K).
zHeat Capacity is the amount of heat required to raise the temperature of a
material one kelvin of temperature. This is unnormalized specific heat (units of J/K).
zSpecific heat is the specific heat capacity of an analyte compared to the
absolute value of the heat flow, divided by the heating rate, and multiplied by a calibration constant.
dH/dt = Cp (dT/dt) or
Cp = [(dH/dt)/(dT/dt)] x E
E = calibration constant
5C/min 10C/min
20C/min
160
180
200
Cp =
E x H x 60 Hr x M
zCp = Specific Heat Capacity (J/g/C) zE = Calibration Constant (dimensionless) zH = Heat Flow (mW) z60 = conversion constant (min sec) zHr = Heating Rate (C/min) zM = Sample Mass (mg)
1) Equilibrate @ 50C 2) Isothermal for 10 min. 3) Ramp 20C/min to 300C 4) Isothermal for 10 min.
zRun Empty Pans to determine background heat flow zSubtract background heat flow from subsequent
profile
zAt temperature of interest, calculate E
E=
sapphire zMeasure sample mass, e.g., 14.20 mg zMeasure Heat Flow at 380K, e.g., 4.60 mW zSubstitute E into equation on page 103.
E H
Cp =
Crystalline polymers contain more order and thus fewer degrees of molecular motion. Less molecular motion results in lower specific heat capacity.
Complex Cp (J/g/C)
110
120
130
140
150
160
Endotherm
66 24 3 0
tg (h)
360
400
420
Polymer PE PP PS
As the steric bulk of the side chain increases, molecular mobility decreases resulting in lower specific heat.
[
1 2 3 4 8
O ( CH2n)
]
Cp (J/g/C) 0.6226 0.6918 0.7088 0.7597 0.7736
# of Methylenes
As the number of methylenes increase, mobility is increased in the polymer, resulting in higher heat capacity.
B. Wunderlich, ATHAS Cp Data Bank, 1985.
DSC: Effect of Copolymer Composition on Specific Heat Capacity of PE/PP Copolymer @ -93C
As PP concentration is increase, the number of methylenes increases, resulting in a rise in specific heat capacity. Also, with randomness comes entropy, increase in mobility, and increase in specific heat capacity.
MDSC Theory
5C/min 10C/min
20C/min
Heat Flow
The magnitude of measured kinetic heat flow is a function of time at a constant temperature.
t1
time
t2
Heat Flow
f(T,t)
Heat Flow
Cp
dT dt
Temperature
Total = Heat Capacity Heat Flow Component (DSC) = Heating Rate Dependent
Apply Stimulus
FTIR NMR
Measure Response
Stimulus
IR Radiation
Response
Absorbance Wavelength Resonance Frequency Angle of Diffraction Amplitude of Heat Flow
Magnetic Field
All Modulated DSC Signals are derived from three measured parameters.
6
GLASS TRANSITION NOTE: ALL TRANSITIONS OF INTEREST ARE CONTAINED IN MDSC RAW DATA SIGNALS MELTING
0.0
-0.2
-0.4
230
P
ACTUAL MEASURED TEMPERATURE
230
220
220
210
210
200
Exo Up
38
39
40
41
42
43
44
45
200
Time (min)
Temperature (C)
AMHF Cp = xK AMHR
Where: AMHF = Amplitude of Modulated Heat Flow AMHR = Amplitude of Modulated Heating Rate K = Heat Capacity Calibration Factor Definition: The amount of heat required to raise the temperature of a material 1C. Calculation: The basis for making the heat capacity measurement in MDSC can be explained from a series of
Cp = K x
0 HF
HFMT
Where: K = Calibration constant HFS = Differential heat flow with sample HFMT = Differential heat flow with empty pans wt = weight of sample
Cp = K x
Where:
K = Calibration constant HFHR1 = Differential heat flow of sample at HR1 HFHR2 = Differential heat flow of sample at HR2 HR2 HR1 = Heating rate 2 = Heating rate 1
10
4 0.2 2 0 -0.2 2 4
0 50
250
-0.6 300
dH = total heat flow dt Cp = measured heat capacity dT = average heating rate dt dT Cp = heat capacity component (Reversing)
dH dT = Cp + f (T, t) dt dt
6 Complex Cp (J/g/C)
0.05
Complex Cp (J/g/C)
HEAT CAPACITY
0
REVERSING HEAT FLOW
-0.05
-4
-0.15
-0.25
Temperature (C)
0.05
-0.1
REVERSING
-0.05
-0.2
-0.15
0.1
0.05
TOTAL REVERSING
0.0
0.05
-0.05
-0.1
-0.05
-0.15
-0.2
-0.15
-0.25
0.00
NOTE: Sensitivity is 100W Full Scale
TOTAL
-0.02
50
100
250
PET/ABS - MDSC
first heat on molded part
PET Tg
8.46mg sample nitrogen purge
ABS Tg
40
60
80
100
120
140
160
180
200
-0.02
-0.001
3 2
1 DERIVATIVE
-0.002
-0.003
-0.004
Temperature (C)
140
Heat Capacity
1.4 100
Temperature
1.2 80
MDSC 0.30C, 40 sec. period 1C isothermal steps
1.0 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
60
Temperature (C)
120
MDSC: PET Heat Capacity During Glass Transition & Cold Crystallization
1.6
COLD CRYSTALLIZATION (First-Order Transition)
100
110
120
130
Temperature (C)
H of Cure
DMA 1Hz
30
4 Heat Capacity
20
10
11.5
Heat Capacity
90
t1/2Cp
X vit = 0.53
2.0 60
exo
1.5
30
200
Thermochimica Acta, 268, 121-142 (1995), Dr. B. Van Mele, et al at Vrije Universiteit Brussels (Belgium)
MDSC: Sample Pans Standard Crimped zLow, Consistent Mass zBest Choice for MDSC Measurements zSolids, Powders, Films zVolatility may be an issue
zUse for liquid/volatile samples zHigher Mass, Less Sensitivity zUse Heat Sink Compound
25 ml/min (He) Faster rates increase noise Slower rates decrease sensitivity, increase baseline curvature
zFlow Purge Gas through Vacuum Port
<
-4
Delta ( V)
-6
-8
-90.29C
287.04C
-10 -200
-100
300
400
157.74C
Cell Constant Calibration Indium Standard Heat: 28.71 J/g Cell Constant: 1.5555 Onset Slope: -40.63 mW/C Cell Number: 319
152
154
160
162
164
-2
-4
zProvides for Accurate Heat Capacity Measurements zUse Either Sapphire Disc (wide temperature range) or
HDPE (polymer melt) zChoose one-point or average values zEffects of Experimental Conditions
1.2
1.1
10 Sec 20 Sec 30 Sec 40 Sec 50 Sec 60 Sec 70 Sec 80 Sec 90 Sec 100 Sec
K(Cp)
0.9 0.8
0.93
0.91
K(Cp)
0.89 40 Sec 50 Sec 60 Sec 70 Sec 80 Sec 90 Sec 100 Sec 0 10 20 30 40 50 60 70 80 90 100 0.87 0.85
Temperature (C)
K(Cp)
0.89 0.88 0.87 0.86 0.85 0.10C 0.25C 0.50C 0.75C 1.00C 1.25C 1.50C 1.75C 2.00C
0.92
0.9
K(Cp)
0.88 1C/min 3C/min 5C/min Isothermal 0.86 0.84 0 10 20 30 40 50 60 70 80 90 100
Temperature (C)
He purge @ 25 ml/min.
1.60 1.50 1.40 K 1.30 1.20 1.2 1.10 1.00 10 20 30 40 50 Period (sec) 60 70 80 90 0.1 100 0.4 0.2 1
0.8