Ca 2016 Tga PDF

Thermogravimetric Analysis (TGA)
Theory and Applications
Presented by Kadine Mohomed, Ph. D

Applications Manager
TA Instruments – Waters LLC
© TA Instruments
1 TAINSTRUMENTS.COM
TGA: Theory and Applications
Part 1
What is TGA?
Calibration and verification
Instrument hardware
Experimental design
2 TAINSTRUMENTS.COM
Part 2
General Applications
Improving Resolution
Kinetics and Activation Energy
Evolve Gas Analysis
3 TAINSTRUMENTS.COM
What is Thermogravimetric Analysis (TGA)?
•Thermogravimetric Analysis
(TGA) measures weight/mass
change (loss or gain) and the rate
of weight change as a function of
temperature, time and
atmosphere.
•Measurements are used primarily

to determine the composition of
materials and to predict their
thermal stability. The technique
can characterize materials that
exhibit weight loss or gain due to
sorption/desorption of volatiles,
decomposition, oxidation and
reduction.
4 TAINSTRUMENTS.COM
What TGA Can Tell You
•Thermal Stability of Materials

•Oxidative Stability of Materials
•Composition of Multi-component Systems
•Estimated Lifetime of a Product
•Decomposition Kinetics of Materials
•The Effect of Reactive or Corrosive Atmospheres
on Materials
•Moisture and Volatiles Content of Materials
5 TAINSTRUMENTS.COM
Mechanisms of Weight Change in TGA
•Weight Loss:
Decomposition: The breaking apart of chemical bonds.
Evaporation: The loss of volatiles with elevated
temperature.
Reduction: Interaction of sample to a reducing atmosphere
(hydrogen, ammonia, etc.).
Desorption.
•Weight Gain:
Oxidation: Interaction of the sample with an oxidizing
atmosphere.
Absorption.
All of these are kinetic processes (i.e. there is a rate at which

they occur).
6 TAINSTRUMENTS.COM
Thermal Stability of Polymers
1: Gas 1 (N2)
2: Ramp 20ºC/min to 650ºC
3: Gas 2 (air)
Gas Switch
7 TAINSTRUMENTS.COM
Oxidative Stability (Polypropylene)
120
––––––– PP Resin Nitrogen
–––– PP Resin Air
285.40°C 431.95°C
100
80
Weight (%)
60
40
20
0
0 200 400 600 800 1000
Temperature (°C) Universal V4.3A TA Instruments
8 TAINSTRUMENTS.COM
TGA of Drug A Monohydrate
105 6
4.946%
(0.7505mg) Decomposition
100
4
Deriv. Weight (%/min)

95
Weight (%)
Water weight loss 2
90
0
85
Sample: Drug A Monohydrate
Size: 15.1740mg
Heating Rate: 10°C/min
80 -2
0 50 100 150 200 250 300
Temperature (°C) Universal V3.4C TA Instruments
9 TAINSTRUMENTS.COM
TGA Data Shows That Acetylsalicylic Acid is
Decomposing Prior to Apparent Melting Point
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Modulated TGA – Decomposition Activation
Energy and Lifetime Kinetics
1,000 110
90
800
] Weight (%)
70
Activation Energy (kJ/mol)
600
50
400
30
[
200
10
Polytetrafluoroethylene
0 -10
400 450 500 550 600
Temperature (°C)
TA Instruments TGA Models
Discovery TGA and Q500/50 Specifications
TGA 5500 Discovery TGA Q500/50
Temperature Range Ambient to Ambient to Ambient to
1200°C 1200°C 1000°C
Isothermal Temperature ±1°C ±1°C ±1°C

Accuracy
Heating Rate Range 0.1 to 500°C/min 0.1 to 500°C/min 0.1 to 100°C/min
(Linear) (Linear) (Linear)
>1600°C/min >1600°C/min
(Ballistic) (Ballistic)
Sample Weight 1000mg 750 mg 1000 mg

Capacity
Dynamic Weighing 1000mg 100 mg 1000 mg
Range
Baseline Dynamic Drift < 10 µg 10 µg <50 µg
(50-1000°C)
Thermogravimetric Analyzers
•A TGA must accurately:

control heating rate (furnace)
measure the change in temperature (thermocouple)
measure the mass of a sample and the change in mass as it is
heated or held at an isothermal temperature (balance)
TGA: Schematic Diagram
Photodiodes
Infrared LED
Meter movement
Balance arm
Tare pan
Sample platform
Thermocouple
Sample pan
Furnace assembly
Purge gas outlet
Heater
Elevator base
Purge gas inlet
Sample pan holder

TGA Balance and Operation
• The balance operates on a

null-balance principle. At the
zero, or “null” position equal
amounts of light shine on the
2 photodiodes.
• If the balance moves out of
the null position an unequal
amount of light shines on the
2 photodiodes.
• Current is then applied to the
meter movement to return the
balance to the null position.
• The amount of current
applied is proportional to the
weight loss or gain.
TGA Furnace Options
TGA Calibration and Verification
•A TGA measures the change in mass of a material with respect to

temperature, time and atmosphere.
•A TGA is calibrated for mass (user), temperature (user) and gas flow
rate control (manufacturer).
•A calibration is affected by
Purge gas and flow rate

Type of specimen pan
Heating rates
International Standards
•American Society of Testing and Materials, ASTM

www.astm.org
•International Organization of Standards, ISO

www.iso.org
•Deutsches Institut für Normung/German Institute for Standardization,

DIN
www.din.de/en
ASTM/ISO Standards for TGA Temperature and
Mass/Weight Calibration
•ASTM E 1582 - Standard Practice for Calibration of Temperature

Scale for Thermogravimetry
•ASTM E 2040 - Standard Test Method for Mass Scale Calibration of

•ISO 11358 – Thermogravimetry (TG) of Polymers
Requirements Prior to Calibration
•The TGA pan should be cleaned prior to calibration procedures. If

using platinum or alumina pans, a flame torch can be used to burn off
organic residue.
•The purge gas flow rate setting should be set (flow rates differ
depending on furnace design and internal volume). The flow rate
should not deviate by more than +/- 5ml/min.
•Use high purity reference materials for calibration
ASTM E 2040 - Mass Scale Calibration of
•The mass signal generated by a TGA is compared to the mass of a

reference material traceable to a national reference laboratory. A linear
correlation using two calibration points is used to relate the mass (or
weight) signal generated by the TGA and that of the reference
material.
• This test method calibrates or demonstrates conformity of

thermogravimetric apparatus at ambient conditions. Most
thermogravimetry analysis experiments are carried out under
temperature ramp conditions or at isothermal temperatures distant
from ambient conditions. This test method does not address the
temperature effects on mass calibration.
•TA Instruments uses a zero tare, then a 100mg and 1000mg mass
standard to calibrate the TGA.
Calibration – Weight (Manual)
Enter the mass of the calibration

weight
Simply reload the mass to verify – mass

difference of ~ 0.005%
Discovery TGA 5500 Baseline Performance
Q 500/50 Baseline Performance
50
Sample Purge 90ml/min of He
20 90
40
Q500 TGA w/ EGA Furnace @ 20°C/min
Balance Purge Flow (mL/min)

Sample Purge Flow (mL/min)
10 Using Recommended Flowrates 80
30
Weight (µg)
26.87µg
0 70
20
-10 60
10
Balance Purge 10ml/min of He
-20 0
0 200 400 600 800 1000
Temperature (°C)
ASTM E 1582 - Calibration of Temperature
Scale for Thermogravimetry
•The standard describes two methods by which the TGA can be
calibrated for temperature; by melting point or magnetic transition.
The most common approach for a TGA would be the magnetic
transition approach.
•Curie Point Temperature - that temperature where the material loses

its magnetic susceptibility - defined as offset point.
•Paramagnetic - a material that is susceptible to attraction by a magnet
•Temperature Calibration points are determined by comparing the

measured melting onset temperature to the literature value
•TA Instruments software allows for up to 5 temperature calibration

points
Generally, these should bracket the temperature range of interest
for subsequent samples
TGA: Temperature Calibration
Vertical Balance Configuration
Tare
Sample
%
Offset
temp
Magnet Attraction of Magnetic Sample to Magnet Results
in Initial Weight Gain, which is lost at the Curie
Transition Temperature
Curie Temperature Reference Materials
•International Confederation for Thermal Analysis and

Calorimetry (ICTAC) developed a set of six certified and
traceable Curie temperature reference materials for the
calibration of TGA and SDT.
•The set consists of Alumel®, nickel, cobalt and three
cobalt/nickel alloys.
•The materials permit temperature calibration in about 200 °C
intervals over the range of 150 to 1120 °C.
•TA Instruments is the exclusive worldwide distributor for
these certified and traceable Curie point materials.
Reference Products for TGA
Curie Temperature Reference Materials

TA Instruments is the exclusive worldwide distributor for a
set of six certified and traceable Curie temperature
materials developed by ICTAC.
Six curie point standards are available

Alumel 153°C
Nickel 358C
Ni83Co17 555°C
Ni63Co37 747°C
Ni37Co63 931°C
Cobalt 1116.0°C
Curie Standards with ICTAC traceability
Calibration – Choose Calibrant, Method is
Automatically Generated
TGA – Temperature Calibration
TGA – Temperature Verification
Calibration – Standard Reference Materials
•Should I expect to obtain the same uncertainty values

observed by the certifying agency?
•Not necessarily!
•What should my uncertainty value be? Where do I start?
•A good place is the precision and bias section associated
with the ASTM method for the analysis – in this case
ASTM E1582.
•ASTM Statement:
How Often Do I Calibrate?
•Protocol is determined by your lab and needs, but there is

no substitute for sound analytical chemistry!
•You simply have to be confident that the data you provide
is correct.
•TA recommends verification on a regular basis.
•Verification is running a known reference material in the
standard operating mode and determining the Curie Point
for temperature and …
•Simply placing a known weight on a tared pan and
checking the mass measured by the balance.
•Control charts allow for statistical monitoring of instrument
performance.
How Often Do I Calibrate? – The Case for
Control Charting
•Example:
Laboratory A has TA Instruments come in for a preventive maintenance
visit every January. This visit includes calibration of the temperature and
mass.
No further calibration or verification is performed until September of the
same year when an internal customer questions the data.
A check of the calibrations shows that the instrument is reading 20 °C too
high and the mass 20 mg too low.
When did the calibration change?
With no verification protocol in place, all of the data for the previous 9
months is considered unreliable. Some protocols require that each client
be notified about the potential discrepancies in their data.
A weekly verification protocol and control chart maintenance would
minimize the amount of suspect data.
Verification of an alumel / nickel calibration takes about 20 minutes.
Verification of the mass calibration using the supplied differential masses
takes less than 10 minutes
Calcium Oxalate “Standard” Analysis
•Although Calcium Oxalate is not generally accepted as a

“Standard Material,” it does have practical utility for
INTRA-laboratory use
•Carefully control the experimental conditions; i.e. pan type,
purge gases/flow rates, heating rate
•Particularly control the amount (~5mg) and the particle
size of the sample and how you position it in the pan
•Perform multiple runs, enough to do a statistical analysis
•Analyze the weight changes and peak temperatures and
establish the performance of YOU and YOUR instrument
•When performance issues come up, repeat the Calcium
Oxalate analysis
Calcium Oxalate Decomposition
•1st Step CaC2O4•H2O (s) CaC2O4 (s) + H2O (g)

Calcium Oxalate Monohydrate Calcium Oxalate
•2nd Step CaC2O4 (s) CaCO3 (s) + CO (g)

Calcium Oxalate Calcium Carbonate
•3rd Step CaCO3 (s) CaO (s) + CO2 (g)

Calcium Carbonate Calcium Oxide
Calcium Oxalate Repeatability
Overlay of 8 runs, same conditions
0.6
100
[ ––––––– ] Deriv. Weight (%/°C)

80
Weight (%)
60
40
20 0.0
0 200 400 600 800
Temperature (°C)
Calcium Oxalate Repeatability
Transition 1 Transition 2 Transition 3

Wt Change Peak Temp Wt Change Peak Temp Wt Change Peak Temp
Run # % °C % °C % °C
1 12.13 156.68 18.78 493.37 29.62 684.33
2 12.22 153.60 18.75 494.17 29.56 680.43
3 12.20 155.40 18.76 495.6 29.63 684.11
4 12.21 155.58 18.77 495.98 29.69 688.11
5 12.21 154.05 18.75 494.72 29.54 684.28
6 12.20 154.91 18.73 495.62 29.58 684.83
7 12.21 155.09 18.77 494.71 29.61 683.92
8 12.20 153.52 18.77 493.84 29.57 681.85
Ave 12.20 154.85 18.76 494.75 29.60 683.98
Std Dev 0.028 1.08 0.016 0.93 0.048 2.24
Theoretical 12.3 19.2 30.1

Accuracy 0.8% 2.3% 1.7%
Precision 0.2% 0.1% 0.2%
Instrumental Considerations
Instrument Hardware and Gas Selection
Considerations
Gas Delivery Module – Discovery TGAs

• Nitrogen - inert, inexpensive and readily available
• Helium - inert, commonly used when performing TGA-MS,
often provides best baseline but will make furnace work
harder at high temperature
• Air/Oxygen - used when studying oxidative stability of
materials, can sometimes improve resolution of weight
loss events
• Gas mixing for specific atmospheres – hydrogen, carbon
dioxide and other gases
TGA Heat Exchanger

• Check cleanliness (no algae growth) once every 3 months
• To clean: empty old water, fill with DI water and add
conditioner (algae growth suppressor) if available
• For Q series, after filling, in software choose “Control \
Prime Exchanger”
TGA: Purge Gas Plumbing
•Mass Flow Controllers

The gas 1 port purges both sample and balance areas. Gas
1 should be an inert gas (N2, He, Ar)
The gas 2 port is used when a different purge gas is
required or gas switching is used. Typically this is air or O2.
Gas type is assigned to Mass Flow Controller in the
Instrument section of the control software and chosen
before on the setup page.
Copper oxalate can be used to detect

any oxygen contamination
Test for Oxygen Contamination of N2 Purge
Gas
Instrument: TGA Q50 V6.7 Build 203
120 6
Copper Oxalate
100 4
Deriv. Weight (%/°C)

Weight (%)
80 2
60 0
10 minute Nitrogen pre-purge

40 -2
0 100 200 300 400 500 600
Effect of Oxygen on Copper Oxalate
65
60
55
Excessive contamination
Weight (%)
6.839%
50 (0.9421mg)
3.561%
(0.4302mg)
45
0.2791%
(0.02653mg)
No contamination
40
10 minute Nitrogen pre-purge

35
200 300 400 500 600 700
Copper Oxalate – Large Mass
100 80
Size = 53mg
10 min prepurge 60
42.5
80

40
42.0
Weight (%)
41.5
400 450 500 550 20
60
40 -20
0 100 200 300 400 500 600
Temperature (°C) Universal V3.3B TA Instruments
Baseline Performance Verification
•A good way to quantify how well the TGA is working

•Especially important for measuring small weight losses
associated with volatilization or small amounts of residue
•Run clean, empty, tared pan, over temperature range of
interest, at desired heating rate
•Plot weight in µg vs. temperature
•Dynamic drift should be less than 10 micrograms for the
Discovery TGA, TGA 5500 and less than 50micrograms on
the Q Series TGA’s when using platinum pans and
20°C/min heating rate
TGA: Factors Influencing Baseline
•Stability of table
•Hang down wire / beam condition
•Hang down tube condition
•Leveling of TGA
•Cleanliness of the furnace
•Purge gas flow rates
Effect of Purge Gas Flowrate on Baseline
50
20 90
40
Q500 TGA w/ EGA Furnace @ 20°C/min

10 Using Recommended Flowrates 80
30
Weight (µg)
26.87µg
0 70
20
-10 60
10
-20 0
0 200 400 600 800 1000
Temperature (°C)
Effect of Purge Gas Flowrate on Baseline

60
70
70
Q500 TGA w/ EGA Furnace @ 20°C/min 50

Using Other than Recommended Flowrates

50 71.63µg
40 60
Weight (µg)
30 30
50
20
10
10
40
-10 Balance Purge 40ml/min of He
0 200 400 600 800 1000

Temperature (°C)
Balance Sensitivity- 120 µg Calcium Oxalate
110
Calcium Oxalate (120µg sample)

100
Note total weight loss = 15µg !!!
12.32%
90 (0.01564mg)
Weight (%)
80
70
60
50 100 150 200 250 300
Temperature (°C)
Sample: 27µg Sodium Tartrate
100
15.56%
80 (0.004201mg)
Weight (%)
60
Sodium Tartrate water loss
literature value : 15.65%
Note : 4µg weight loss clearly detected !!!!
40
60 80 100 120 140 160 180
Temperature (°C)
TGA: High Sensitivity Volatiles Analysis
100.1 2.4 mg PET Bottle

2.4 mg PET
10°C/min
10C/min
100.0
Weight (%)
0.2162% Volatiles
99.9 (0.005198mg)
99.8
99.7
20 40 60 80 100 120 140 160 180
Universal V3.9A TA Instruments
Temperature (°C)
TGA: Sample Preparation
•Sample mass
10-20mg for most applications
50-100mg for measuring volatiles
•If a TGA has a baseline drift of +/-25µg then this is 0.25% of a
10mg sample
TGA particle size matters, NaCl decrepitation
0.06
100.0
0.05
0.04

99.5
Weight (%)
0.03
99.0 0.02
0.01
98.5
0.00
98.0 -0.01
0 100 200 300 400 500 600
Temperature (°C)
TGA: Sample Preparation
•Use brass tweezers to eliminate static effects

•Tare a clean sample pan before every run
•Distribute sample evenly over bottom of pan
•Liquid samples - use hermetic pan with a pin-hole lid
TGA: Sample Pans - Types/Sizes
Platinum Ceramic (alumina)
Aluminum
500 µL
50 µL 250 µL
100 µL 80 µL 100 µL
Deep-walled pans are good for larger mass and low-density materials
TGA: Sample Pan Selection
•Platinum (useful for most materials)

Easy to Clean
Nonporous
Bu can alloy with most metals
•Alumina (Ceramic)
Corrosives/Inorganics
Large samples
•Aluminum (TGA) (designed for one-time use)
Lower cost, disposable
Lower temperature limit (<=600°C)
Sealed Aluminum Pans
Sealed Aluminum Pans and Punching
1. Home Position
2. Pre-Punching
Punch
Force
3. Punching Sensor
TGA: Sample Pan Cleaning
•All sample pans are reusable

(except Aluminum)
•Flame remaining residue from pan with torch
(do not flame Aluminum pans)
•Scrape off remaining ash (DSC fiberglass brush)
TGA: Environment Considerations
•Avoid areas near heater or air conditioner ducts

•Avoid tables with drawers or those near a door
•For optimum results, use a marble table
Experimental Methods
Experiment Setup
•Experiments are created in

the Running Queue or the
Design View.
•They are launched from the
Running Queue!
Experiment Setup
•Sample information is entered here
Experiment Setup
Experiment Setup
Segment Statements
•The logic of the instrument control software is based upon

segment statements which the user enters during the
design of the experiment.
•These segments are executed during the experiment.
Method Segments
Method Design: TGA
Segment List
•The Ramp segment heats or cools the
sample at a fixed rate until it reaches the
specified temperature, producing a linear
plot of temperature versus time
•The Equilibrate segment heats or cools

the furnace to the defined temperature,
stabilizes the furnace at that temperature,
then continues to the next segment.
•The Select Gas segment controls the

switching of gas between Gas 1 and Gas
2 for an instrument with a gas delivery
module. This segment is used to
synchronize gas switching at a specific
time or temperature in an experiment.
Segments and Descriptions
Segments and Description
Typical Methods
•Ramp (heating) experiment:

Ramp 20°C/min. to 800°C
•Ramp and switch gas

(carbon black content,
residue)
Select gas: 2
Ramp 20°C/min. to
1000°C
Typical Methods – Ramp and Isothermal Hold
Typical Methods
•Ramp and switch gas (carbon black content)

Select gas: 2
•High Resolution Ramp

Ramp 50°C/min. res 5 to 800°C
(resolve closely spaced peaks)
General Considerations
Experimental Effects
TGA Curves are not ‘Fingerprint’ Curves
•Because most events that occur in a TGA are kinetic in

nature (meaning they are dependent on absolute
temperature and time spent at that temperature), any
experimental parameter that can effect the reaction rate
will change the shape / transition temperatures of the
curve.
•These things include:
Sample Mass
Heating Rate
Purge gas
Sample volume/form and morphology
Larger sample mass increases the observed
decomposition temperature
Polystyrene 17.6 mg
100 Polystyrene 10.2 mg
Polystyrene 5.4 mg
Polystyrene 2.7 mg
80
60
Weight (%)
40
20
0 100 200 300 400 500 600

Temperature (°C) Universal V4.2D TA Instruments
Higher heating rates increase the observed
decomposition temperature
Polystyrene 20°C/min
100 Polystyrene 10°C/min
80
Sample Mass
10mg ±1mg
60
Weight (%)
40
20
0 100 200 300 400 500 600

Temperature (°C) Universal V4.2D TA Instruments
Sample Morphology Effects – PET
12 0
419.58°C 424.58°C
10 0
80
Weight (%)
60 2.9 mg; amorphous PET

2.9 m g; am orphous P E T
2.82.8
mg; semi-crystalline
m g; crystalline P ET PET
40
20
0
0 10 0 2 00 30 0 4 00 5 00 60 0
Temperature (°C ) Universal V3.8A TA Instrum ents
High-Heating Rate TGA Analysis
100
80
60.09% Polypropylene
(2.736mg)
40°C/min 500 °C/min

Weight (%)
60
40
40% calcium
carbonate
20
0
0 200 400 600 800 1000
Universal V3.9A TA Instruments
Temperature (°C)
High-Heating Rate TGA Analysis
What if I need help?
•TA Tech Tips

http://www.youtube.com/tatechtips
•Call the TA Instruments Hotline

302-427-4163 M-F 8-4:30 Eastern Time
thermalsupport@tainstruments.com
•Visit our Website

http://www.tainstruments.com/
On-site training & e-Training courses
Practical Series Webinars
Part II - Applications
Part 2
General Applications
Improving Resolution
Kinetics and Activation Energy
Evolve Gas Analysis
Basic Applications
Thermal Stability of Polymers
1: Gas 1 (N2)
3: Gas 2 (air)
Gas Switch
Block versus Random Copolymers
Effect of Epoxy Cure Temperature
Residue Determination - 0.2% Salt Solution
100
Sample: NaCl – 0.2% in H2O

Size: 97.6300mg
80
Method Log:
1: Ramp 5.00 °C/min to 90.00 °C
2: Isothermal for 120.00 min
3: Ramp 5.00 °C/min to 600.00 °C
4: End of method
60
Weight (%)
40
20
Residue:
0.2212%
(0.2160mg)
0
0 50 100 150 200 250
Time (min) Universal V3.2A TA Instruments
TGA of Drug A Monohydrate
105 6
4.946%
(0.7505mg) Decomposition
100
4

95
Weight (%)
Water weight loss 2
90
0
85
Sample: Drug A Monohydrate
Size: 15.1740mg
80 -2
0 50 100 150 200 250 300
Temperature (°C) Universal V3.4C TA Instruments
EVA Copolymer
120
16.87% Acetic Acid

100 (3.240mg)
80
% Vinyl Acetate = % Acetic Acid *

Molecular Weight(VA) / Molecular
60
Weight (%)
Weight (AA)
40 VA% = 16.85(86.1/60.1)
= 24.2%
20
Sample: EVA (25%)

0
Size: 19.2030mg
-20
0 100 200 300 400 500 600 700
Temperature (°C) Universal V3.3B TA Instruments
PET w/Carbon Black Filler
2.0
100
C arbon Black F illed PE T

How much
1.5
80 Carbon Black
was in this
sample?

60 1.0
Weight (%)
40
78.64%
0.5
(11.26m g)
20
0.0
In N 2
20.00 °C /m in to 650.00 °C 20.64%
Switch to A ir (2.957m g)
R am p 20.00 °C /m in to 1000.00 °C
0
-0.5
0 200 4 00 600 800 100 0
Temperature (°C)
PET Without Filler
2.0
100
PET
1.5
80

60 85.65% 1.0
(16.01m g)
Weight (%)
40 0.5
20
0.0
In N 2 13.99%
20.00 °C /m in to 650.00 °C (2.614m g)
S witch to A ir
0 R am p 20.00 °C /m in to 1000.00 °C
-0.5
0 200 400 600 800 1000
Temperature (°C )
Comparison of Filled & Un-Filled PET
PET
100 F ille d P E T
80
60
6 .6 5 % C a rb o n B la c k
Weight (%)
40 7 8 .6 4 % 2 0 .6 4 %
(1 1 .2 6 m g ) (2 .9 5 7 m g )
20
M e th o d L o g :
1 : R a m p 2 0 .0 0 °C /m in to 6 5 0 .0 0 °C 8 5 .6 5 % 1 3 .9 9 %
2 : S e le c t g a s : 2 (1 6 .0 1 m g ) (2 .6 1 4 m g )
3 : R a m p 2 0 .0 0 °C /m in to 1 0 0 0 .0 0 °C
0
0 200 400 600 800 1000

T e m pe ra ture (°C )
Composite Analysis
EPDM Rubber Analysis
Filled Polymer Analysis
100
(A)
Polymer Air
Carbon Black
Inert filler
0
100 "Light" Oil
(B)
WEIGHT (%)
Polymer Air
Carbon Black
0 Inert filler
100
Polymer +
(C)
"Heavy" Oil Air
Carbon Black
0 Inert filler
TEMPERATURE (°C)
Effect of Flame Retardant
100
Without Flame Retardant
90
With Flame
Retardant
WEIGHT (%)
80
70 Size: 20 mg
Prog.: 10°C/min
Atm.: Air
60
0 200 400 600 800

TEMPERATURE (°C)
TGA-MS of Flame Retardant
100
80
60
MS Intensity
Benzene
PVC
TGA Weight (%)
40 PVC + MoO
3
(78 amu)
20
0 100 200 300 400 500 0 100 200 300 400 500
Temperature (°C) Temperature (°C)
Benzene is a component of smoke. Much

reduced in the flame retardant sample. TAINSTRUMENTS.COM
Vegetable Oil Oxidative Stability
Similar principle to OIT experiment done by DSC
137
+
125
Sample Size: 5.18 mg
Temperature: 137°C
WEIGHT CHANGE
Atmosphere: 02 0.05 100
TEMP (°C)
02
75
57 MINUTES
FIRST DEVIATION 50
25
-
0 10 20 30 40 50 60 70 80 90
TIME (Min.)
TGA Resolution
TGA Resolution
Introduction: Methods to change

temperature in a TGA experiment
Improving resolution in Standard

(constant heating rate) TGA experiments
Hi-ResTM TGA
Automated Stepwise isothermal TGA
Temperature-controlled TGA (standard TGA)
vs sample-controlled TGA
Temperature-controlled thermal analysis Sample-controlled thermal analysis
Ref:
O. Toft Sørensen and J. Rouquerol (2003). Sample Controlled Thermal Analysis: Origin, Goals, Multiple Forms, Applications
and Future. Kluwer Academic Publishers, Netherlands
Standard TGA: advantages
• Easy to set up
• When the individual decomposition steps occur at well-separated
temperatures, quantitative information for each step can be obtained
Standard TGA: limitations
•Complex thermal scans with broad weight losses

•Overlapping weight losses
Multiple peaks/shoulders
Standard TGA of bitumen
120 0.8
d(Weight) / d(Temperature) d(Weight ) / d(

0.7
100
0.6
80
0.5
Weight (%)
60 0.4
40 0.3
0.2
20
0.1
) ((%) / (°C))
0
0.0
-20 -0.1
0 100 200 300 400 500 600 700 800
Temperature (°C)
Ref:
112
J-F. Masson, S. Bundalo-Perc, Thermochimica Acta, 436 (2005), 35–42 TAINSTRUMENTS.COM
Improving resolution in Standard TGA
experiments
• Means of Enhancing Resolution
Slower heating rate

Reduced sample size
Pin-hole hermetic pans (self-generating atmosphere)
Impact of heating rate on resolution: 20°C/min
110 10
20°C/min
) Deriv. Weight (%/min)

100
13 minutes
6
Weight (%)
90
4
80
2
WATER
70
0
(
60 -2
0 50 100 150 200 250 300
Temperature (°C)
Impact of heating rate on resolution: 1°C/min
100 1.0
1°C/min
170 MINUTES
0.8
) Deriv. Weight (%/min)

90
0.6
Weight (%)
80 0.4
0.2
70
0.0
(
60 -0.2
0 50 100 150 200 250 300
Temperature (°C)
Effect of sample mass on resolution: bitumen
Ref:
116
Resolution enhancement using a pinhole
hermetic DSC pans
Pt TGA pan
Tzero Hermetic Pinhole Lid

(75 µm laser drilled pinhole)
Tzero pan
Resolution enhancement using a pinhole
hermetic DSC pans: gypsum
• Heating gypsum between 100°C and 150°C (302°F) partially
dehydrates the mineral by driving off exactly one and a half moles of
the water contained in its chemical structure.
•The partially dehydrated mineral is called calcium sulfate hemihydrate

or calcined gypsum (CaSO4·½H2O).
CaSO4·2H2O + heat → CaSO4·½H2O + 1½H2O (steam)

• As heating continues, the anhydrite, CaSO4, is then formed.
CaSO4·½H2O + heat → CaSO4+ ½H2O
Theoretical Mass Losses of Gypsum
• CaSO4·2H2O + heat → CaSO4·½H2O + 1½H2O

A loss of 1½H2O = 100*(MW. 1½H2O/ MW. CaSO4·2H2O)
= 15.69%
• CaSO4·½H2O + heat → CaSO4+ ½H2O

A loss of ½H2O = 100*(MW. ½H2O/ MW. CaSO4·2H2O)
= 5.23%
• Total weight loss = 15.69% + 5.23% = 20.92% (2 mols

H2O)
Effect of DSC Pinhole pans on TGA resolution
Gypsum
105 2
Theoretical: 15.69%
14.90%
[ – – – – ] Deriv. Weight (%/°C)

95
(1.050mg)
Theoretical: 5.23%
4.830%
Weight (%)
85
(0.3405mg)
Standard 1
TGA Pan
75
65 Pin Hole
DSC Pan
55 0
0 50 100 150 200 250
Temperature (°C)
Sample-controlled TGA to improve TGA
resolution
Hi-ResTM TGA
• In a Hi-ResTM TGA experiment the heating rate is controlled by the rate of

decomposition.
• Faster heating rates during

periods of no weight loss, and
slowing down the heating rate
during a weight loss – therefore
not sacrificing as much time
• Hi-ResTM TGA can give better

resolution or faster run times,
and sometimes both
Hi-ResTM TGA of Calcium oxalate
calcium oxalate - Hi-ResTM TGA
1.75 110 100

50°C/min, resolution 5, sensitivity 1
1.50 100
1.25 90 50
1.00 80
0.75 70 0
0.50 60
0.25 50 -50
0.00 40
-0.25 30 -100
0 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)
Hi-ResTM TGA vs. Std TGA of Nylon/PE Blend
100
Std TGA 1°C/m in
Tim e = 771.46 m in
80 Hi-Res TGA 50°C/m in; Res 5

Tim e = 125.29 m in
Std TGA 20°C/m in

60
Weight (%)
Tim e = 38.64 m in
40
20
0
0 200 400 600 800
Temperature (°C) Universal V2.5D TA Instrum ents
Programming a Hi-ResTM TGA experiment –
sensitivity number
1. Sensitivity 1.0
2. Ramp 50°C/min, Res. 4.0 to 1000°C
Sensitivity : typically varies from 0 to 8.0
Controls the response of the Hi-Res system to

changes in decomposition rates (∆ wt%/min)
Determines the increase in decomposition rate

that warrants a reduction in the heating rate (or
vice-versa)
Higher sensitivity values make the Hi-Res

system more responsive to small changes in the
125
rate of reaction TAINSTRUMENTS.COM
Programming a Hi-ResTM TGA experiment –
resolution number
1. Sensitivity 1.0
2. Ramp 50°C/min, Res. 4.0 to 1000°C
Resolution : typically varies from -8.0 to 8.0
Adjusts the heating rate based on the

sample decomposition rate (wt%/min)
As the decomposition rate increases, the

heating rate is further decreased (and vice-
versa).
Higher resolution number (absolute value)

results in a greater reduction in heating rate
126
at smaller values of wt%/min TAINSTRUMENTS.COM
Effect of sensitivity settings on TGA data
Res = 5 for all Hi-Res experiments
1 C/min std TGA
Sensitivity setting 1
Effect of resolution settings on TGA data
Hi-Res TGA on ethylene-vinyl acetate copolymer
Sensitivity = 1 for all curves
Resolution = 1
Sensitivity = 1
Resolution = 8
Sensitivity = 1
Resolution: 8 Resolution: 1
Note that increasing resolution setting increases the resolution of each transition and
simultaneously reduces the transition temperature.
Optimizing the Hi-ResTM TGA settings
• Sensitivity of 1 and resolution of 4 are good starting

points. Higher resolution number means slower heating
rate.
• Increasing the resolution number if you need further

separation of derivative peaks
Two modes of Hi-ResTM TGA
Hi-ResTM TGA
Constant
Dynamic mode
reaction mode
(wt%/min is
(wt%/min is
variable)
constant)
Compare Hi-ResTM TGA vs. standard TGA at
10°C/min – Ethylene Vinyl Acetate copolymer
Use of Hi-ResTM TGA for determination of free
and bound water in pharmaceuticals
Standard TGA Hi-ResTM TGA
Note the use of 10 C/min heating rate in the Hi-ResTM TGA as the sample loses mass
rapidly
Ref:
132
TA Instruments application note TS17 TAINSTRUMENTS.COM
Standard TGA 10°C/min of bitumen sample
120 0.8
d(Weight) / d(Temperature) d(Weight ) / d(

air purge
Middle 0.7
Higher
100 Temp
Temp
Region
Region
0.6
80
0.5
Weight (%)
60 0.4
Lower
Temp
40 Region 0.3
0.2
20
0.1
) ((%) / (°C))
0
0.0
-20 -0.1
0 100 200 300 400 500 600 700 800
Temperature (°C)
Ref:
133
Standard TGA vs Hi-Res TGA (dynamic mode)
of bitumen sample
1.25
standard TGA
1.00 Hi-res TGA - dynamic mode
0.75 Heating rate: 50 C/min

Res: 3
0.50 Sen: 5
0.25
0.00
-0.25
-0.50
-0.75
-1.00
0 100 200 300 400 500 600
Ref: Temperature (°C)
134
Constant Reaction Rate TGA of bitumen sample
1.0
Hi-res TGA - constant reaction rate
standard TGA
dm/dt = 0.316%/min
resolution: -4,
sensitivity: 1
0.5
0.0
150 200 250 300 350

Ref: Temperature (°C)
135
Hi-ResTM TGA- Advantages
•Relatively simple to develop method

•Rapid survey over wide temperature range with excellent
resolution
•High resolution with equal/better productivity, even on
unknowns
Automated Stepwise Isothermal TGA (SWI)
•Heating stops (goes isothermal) when a certain rate of

weight loss is reached, then resumes after this rate falls
below a second defined value
•Operator defines the values for the rate of weight loss
•Incorrect values can cause artifacts that appear as
‘additional’ mass losses
•Correctly set up, can give excellent resolution, but takes
quite a bit longer
Automated Stepwise Isothermal TGA (SWI)
•Advantages
Sample held isothermal until transition completed - thus
excellent resolution of overlapping transitions
Permits careful control of reaction environment
Programmable on any TGA
•Disadvantages
Requires method development. May require several scans
to optimize run conditions
Inappropriate parameter choices may produce artifacts
Long run times
Standard TGA of Polyvinyl Acetate
Basis for Entrance

Threshold
Ref:
Thermal Applications Note TN40 – Optimizing Stepwise Isothermal Experiments in
139 Hi Res TGA TAINSTRUMENTS.COM
Typical SWI Thermal Method
1. Abort next segment if %/min > 4

2. Ramp 10°C/min to 1000°C
3. Abort next segment if %/min < 0.4
4. Isothermal 1000 min
5. Repeat 1 until 1000°C
SWI of Polyvinyl Acetate
Ref:
Thermal Applications Note TN40 – Optimizing Stepwise Isothermal Experiments in
141 Hi Res TGA TAINSTRUMENTS.COM
Hi-ResTM TGA of lubricating oil (Res. 4)
120 2.0
24.72% First Weight Loss Event

(2.959mg)
359.23°C
100 1.5

39.05% Second Weight Loss Event
80 (4.674mg) 1.0
Weight (%)
60 254.73°C 0.5
40 0.0
Time (min)
0 10 20 30 40 60 70 80 85
20 -0.5
0 200 400 600 800 1000
Hi-ResTM TGA of lubricating oil (Res. 6)
120 2.5
325.71°C
(2.854mg) 2.0
100
1.5

80 (5.012mg)
Weight (%)
1.0
60 205.52°C
0.5
4.357% Third Weight Loss Event
(0.5488mg)
412.42°C
40
0.0
Time (min)
0 25 100 150 250 300 325 343
20 -0.5
0 100 200 300 400 500 600
Stepwise Isothermal TGA of lubricating oil
120

(2.623mg)
100

80 (4.231mg)
Weight (%)
60
5.655% Third Weight Loss Event

(0.6660mg)
40
Time (min)
0 25 75 250 255
20
0 100 200 300 400 500 600
TGA
Decomposition Kinetics
Decomposition Activation Energy by MTGATM
How is decomposition
kinetics measured by TGA?
Conventional method for

Activation Energy
A guide to Modulated TGA
Applications of MTGA for

Kinetic Analysis
•The rate at which a kinetic process proceeds depends not

only on the temperature the specimen is at, but also the
time it has spent at that temperature.
•Typically kinetic analysis is concerned with obtaining
parameters such as
activation energy (Ea),
reaction order (n), and
generating predictive curves for conversion ().
Kinetics by TGA
−

: =
−
Initial weight:
win 100
Weight at T:
Conversion, %
wT
Weight, %
α
Final weight:
wf 0
T
Kinetic Analysis
Activation energy (Ea) can be defined as the minimum amount of energy

needed to initiate a chemical process.
State 1
Ea
State 2
Introduction: Decomposition Kinetics
Thermal decomposition kinetics can be represented by the

following generic kinetic equation:
%&
= ( )(+), where:
%'
α - conversion fraction (normalized weight on a TGA curve)

%&
- rate of conversion (rate of weight loss on a TGA curve)
%'
f(α) - rate function dependant upon conversion fraction
k(T) - rate function dependant upon temperature
Almost without exception this is taken to be the

Arrhenius equation, so:
-
= ( /
012 ⁄3
-.
α - conversion fraction (normalized weight on a TGA curve)

%&
- rate of conversion (rate of weight loss on a TGA curve)
%'
f(α) - rate function dependant upon conversion fraction
/ - pre-exponent factor
Ea - activation energy
R - gas constant
Decomposition Kinetics by TGA
•Traditional methods include isothermal and constant

heating rate techniques.
•ASTM E1641
Based on method of Flynn and Wall – Polymer Letters, 19,
323 (1966). Requires collection of multiple curves at
multiple heating rates.
Weight (%)
Increasing
Heating Rate
Heating rate:
-+
6=
-.
Thus
- / 01 ⁄3
=
2 (
-+ 6
For a single heating rate:
- 6
7 = 7 / −89 ⁄:+
-+ (
At a select α conversion
- 7 - ⁄-.
= −89 ⁄:
-+ 0; &
Recipe for Activation Energy by ASTM E1641.
Polymer Decomposition
• Run TGA experiment on polymer at 4-6 different heating rates
• Obtain a temperature at an isoconversional point – for

example 10% weight loss for each heating rate
• Plot the ln of the heating rate (β

β) versus 1/T (temperature
units must be in Kelvin)
• Slope of the line is (-E

Ea/R). Multiply the slope of the line by –
(8.314 x 10-3) to obtain the activation energy in kJ/mol.
TA Instruments Application Note TA251

Blaine, R. L. and Hahn, B. K., “Obtaining Kinetic Parameters by Modulated Thermogravimetry,” J.
Therm. Anal., Vol. 54, 1998, p. 694.
PTFE Decomposition by ASTM E1641
10 % Conversion
Temperature at
10 % Weight
Heating Rate (β
β) °C / min ln (β) Loss (°C) 1/T (K)
10 2.303 532.98 0.001240
8 2.079 529.54 0.001246
6 1.792 525.53 0.001252
4 1.386 519.36 0.001262
2 0.693 509.48 0.001278
1 0.000 499.30 0.001295
Intercept of ln(β
β) vs 1/T 55.25
Slope of ln(β
β) vs 1/T -42685
Activation Energy Ea
354.9
(kJ/mol)
Peaks
Temperature is altered between

Temperature is alternated between 245 and 247°C.
T2 245 and 247 ºC
Valleys
Temperature (°C)
T1
Conversion values ~ constant.
158 *J.H. Flynn, Thermal Analysis, R.F. Schwenker and P.D. Garn, Eds., Academic Press, Budapest, 2, 1969, 1111-1123 TAINSTRUMENTS.COM
Solution for Ea Assuming Constant Conversion
From the general rate equation at each temperature T1 and T2 :
-⁄-. ? = ( /
012 ⁄3? and -⁄-. @ = ( /
012 ⁄3@
Assuming f(α) is the same (constant conversion values), take the ratio
and solve for Ea:
-; ⁄-A =
012 ⁄3 ;⁄?0;⁄@
: 7 -; ⁄-A
89 =
1⁄+A − 1⁄+;
This method is called the Factor Jump Method.
PS: Temperature Step Change Experiment
Temperature isotherms
between 300
Temperature and
Isotherms 305300ºC
between and 305°C.
89.55%
89.55%
90.03%
90.03%
0.40 %/min
0.40%/min
0.32%/min
0.32 %/min
Ea = [8.314ln(.0032/.004)]/(1/578-1/573)
Ea = 122.9 kJ/mole at 10% conversion
Proceed from Step Change to Sinusoidal
Change in Temperature
For sinusoidal temperature:
T = Ti + Ta sin(ωt)
Ti - isothermal temperature
Ta - modulation amplitude
For peak and valley temperatures:
TP = Ti + Ta TV = Ti - Ta
After substitution and rearrangement
+ A − +9 A
89 = : 7 -; ⁄-A
2+9
PS: Quasi-Isothermal Experiment @ 290°C
112.4kJ/mol
112.4 kJ/mol
90.0 %
90.00%
Extension to Modulated Temperature Ramping
Advantages of MTGATM
•One run needed to obtain activation energy.
•Activation energy is a signal in the data file.
•Comparable with Flynn-Wall method for calculated Ea with the benefit

of the reduced time.
•Method works under quasi-isothermal or ramping conditions.
•Activation energy is obtained as a continuous curve and so can be

manipulated numerous ways. For example, it can be plotted as a
function of conversion.
•Can be combined with Hi-Res™ to speed up experiments and more

accurately handle multiple weight loss events.
Setting Up MTGATM Experiment
• Three parameters must be defined:

• heating rate
• modulation period
• modulation amplitude
• What is the effect of these parameters on the data? What are the optimum
values?
General Guidelines
•Higher amplitudes improve signal/noise and increase

precision, but require longer periods to make sure the
sample is remaining in equilibrium.
•Longer periods ensure equilibrium, but require slower ramp

rates so the minimum 5 cycles per transition can be
obtained.
•A scouting run at 10 °C/min is useful to determine width of

transitions.
•Range of consistent results:

Period = 200-300 s (practical range: 100 – 500s)
Amplitude = 3-5 °C (practical range: 1 – 10 °C)
Ramp Rate = 1 °C/min (practical range: 0.5 – 2 °C/min)
MTGATM – Typical Values
•Modulation period – 200 seconds.

•Amplitude – 4-5°C.
•Heating rate – 1 to 2 °C/min.
•Plot derivative of weight loss and calculate the width at
half height of the derivative weight loss peak.
Need at least 5 modulation cycles across this region.
Weight (%)
PTFE: Modulated Ramping Experiment
Negligible Negligible
weight change
Polytetrafluoroethylene weight
change
MTGA Precision: PTFE
Standard Relative
Conversion Average Deviation Stnd Dev
(%) #1 #2 #3 #4 #5 (kJ/mol) (kJ/mol) (%)
1 333.0 342.4 335.8 345.9 340 339.42 5.14 1.51
2 334.9 329.3 330.8 330.8 327.7 330.70 2.67 0.81
5 319.3 322.6 323.7 319.7 323.1 321.68 2.03 0.63
10 313.1 314 311.9 316.2 318.6 314.76 2.66 0.85
Repeatability = 2.8X Standard Deviation
C.G. Slough The Accuracy, Repeatability, and Reproducibility of Activation Energy Values Measured by
Modulated Thermogravimetry. J of Testing and Evaluation V. 42, N. 6 (2014)
Decomposition of PP by Flynn-Wall Method
270
Atmosphere Ea* / kJ mol-1
240 N2 244
-1
N2 216
Eα / kJ mol
N2 214
210
N2 160
N2 115 – 200
180 N2 130 – 200
N2 230
150 Vacuum 257
Ar 98, 328
0.0 0.2 0.4 0.6 0.8 1.0
* Data obtained from multiple publications
α
Thermal Analysis of Polymers: Fundamentals and Applications. Chapter 3. Edited by by J. Menczel and R. B.
Prime (2009)
PP: Modulated Ramping Experiment
Literature: Ea = 232 ± 27 kJ/mol (12 % standard deviation)

This study: Ea = 200 ± 19 kJ/mol (standard deviation 9.5 %)
PP: Modulated Ramping Experiment
TGA Kinetics - Estimated Lifetime
TEMPERATURE (°C)
260 280 300 320 340 360
1000000
1 century
100000 1 decade
ESTIMATED LIFE (hr.)
ESTIMATED LIFE
10000 1 yr.
1000 1 mo.
1 week
100
1 day
10
1.9 1.8 1.7 1.6 1.5
1000/T (K)
TA Instruments Application Note TA125
Estimation of Polymer Lifetime by TGA Decomposition Kinetics
TGA Kinetics
• ASTM committee E37 on Thermal Methods is currently

developing a standard for kinetics by either the Factor
Jump method or MTGA
• Modulated TGA is a comprehensive method to obtain an

activation energy of decomposition in a single run
• Data by MTGA is comparable to that of the Flynn-Wall

method
• It can be a powerful tool to compare energetics of similar

systems (for example, composites of close compositions,
polymers with additives)
Evolved Gas Analysis
Identification of Decomposition Products

Using TGA/FTIR and TGA/Mass Spec
Why Use Evolved Gas Analysis?
•TGA measures weight changes (quantitative)

•Difficult to separate, identify, and quantify individual
degradation products (off-gases)
•Direct coupling to identification techniques (Mass Spec,
FTIR) reduces this problem
TGA-EGA: Typical Applications
•Polymers (composition, hazard evaluation, identification)

•Natural Products (contamination in soil, raw material
selection {coal, clays})
•Catalysts (product/by-product analysis, conversion
efficiency)
•Inorganics (reaction elucidation, stoichiometry,
pyrotechnics)
•Pharmaceuticals (stability, residual solvent, formulation)
TGA / FTIR
• Advantages • All of the Advantages of

– No solvents TGA/MS
– No sample preparation – Search capabilities are
– Rugged really good – Thermo
Nicolet for example
– Easy maintenance
– Data interpretation can be
– Good sensitivity challenging.
– Easy to use – Generally, with EGA
– Excellent for scouting or analysis, a strong
determining presence of chemistry and analytical
absence of species chemistry background is
– Fast identification of needed.
functional groups
EGA Example – TGA/FTIR
•The gases produced during thermal breakdown of the sample flow

through a heated transfer line into a gas cell where infrared radiation
passes through.
•The total infrared absorption and frequency as a function of time is
stored in an array as the Gram Schmidt file which is opened with the
instrument software (Gram Schmidt Reconstruction).
•The Gram Schmidt reconstruction will typically resemble the derivative
with respect to temperature of the weight loss curve in the TGA
experiment.
•Individual FTIR spectra are displayed by selecting points on the x-axis
of the Gram Schmidt reconstruction which has units of intensity as a
function of time.
•Typically spectra can be searched using vendor supplied spectral data
bases and fairly reliable identifications of species can be made.
EGA Example – ID of Components of Fuel
Additive by FTIR
2.0
100
33.35%
(13.18mg)
80 1.5

9.266%
(3.663mg)
60
Weight (%)
16.06%
(6.350mg)
1.0
40
17.87%
(7.065mg)
20 0.5
19.03%
(7.525mg)
Residue:
4.158%
(1.644mg)
0
0.0
0 100 200 300 400 500 600
Additive by FTIR
Gram Schmidt Reconstruction
Additive by FTIR – Peak 1
Aromatic Hydrocarbons
Mixture of Aromatic and Aliphatic

Hydrocarbons
Aliphatic
Hydrocarbons
Aliphatic
Hydrocarbons
Ammonia gas, possible

HCN, and Aliphatic
Hydrocarbons
Additive by FTIR
•Peak 1 – Various aromatics. Appear to be highly substituted ring
structures. Sum tone pattern is not obvious, nor is there strong
evidence for only monosubstitution.
•Peak 2 – Various Aromatics – very similar to peak 1, but
evidence of different substitution patterns on the ring. Possibly
different dimethyl and tertiary butyl groups (as ring substituents)
as well.
•Peak 3 – Highly branched aliphatics, similar to isoalkenes
(isobutene, for example). Strong evidence of vinylidene and
vinyl terminal groups, no evidence of long chained
hydrocarbons. This is most likely a highly branched alkene
additive which is to be expected as part of a fuel. Also, there is
some evidence of ammonia gas.
•Peak 4 - Almost identical to Peak 3 with a possible increasing
ether functionality. Less evidence of ammonia gas.
•Peak 5 – Aliphatic alkenes, ammonia gas, evidence of
isocyanate, and possibly hydrogen cyanide
Mass-Spectrometry Benefits
•Additional information for the interpretation of the reactions

in the TGA results
•Sensitive method for the analysis of gaseous reaction
products
•Exact control of the furnace atmosphere before starting
and during the experiment
•Location of air leaks around the furnace
Discovery Mass Spectrometer – TGA / MS
• Advantages • Disadvantages
– No solvents – No search capability
– No sample preparation – Data interpretation can be
– Rugged challenging (as with any
– Easy maintenance unit mass spectrometer)
– Good sensitivity – Multiple software platforms
for data reduction
– Easy to use
– Excellent for scouting or
determining presence of
absence of species – great
complement to GC / MS
TGA-MS: System Schematic
The Discovery Mass Spectrometer (DMS)
• Benchtop, unit resolution

quadrupole mass spec designed
and optimized for evolved gas
analysis (EGA)
• Quadrupole detection system

includes…
a closed ion source
a quadrupole mass filter
assembly
dual detector system (Faraday
and Secondary Electron
Multiplier)
…ensuring excellent sensitivity
from ppb to percent concentrations
TGA / MS
•Gases formed during the TGA experiment are drawn down

a heated transfer line into the mass spectrometer where
they are ionized by an ion stream from the ion source,
sorted by the quadrupole mass filter and ultimately
amplified and detected.
What is a Quadrupole Mass Spectrometer?
A Quadrupole Mass Analyzer

• Ionizes gas molecules and atoms
Electron impact knocks off an electron
and fragments molecules forming
positive ions
• Sorts by the mass/charge (m/z) ratio

• Measures the ion current
• Displays ion current vs. m/z ratio
• When calibrated against inlet pressure
- can display partial pressure vs. m/z
ratio
TGA-MS Example: Aspirin
Sample of TGA Application Briefs
•H-16781 “Thermogravimetry-Mass Spectrometry Using a Simple

Capillary Interface”
•TA023 “Thermal Analysis Review: High Resolution TGA - Theory and
Applications”
•TA075 “High Resolution TGA Kinetics”
•TA 122 “Determination of Carbon Black Pigment in Nylon 66 by TGA”
•TA 125 “Estimation of Polymer Lifetime by TGA Decomposition
Kinetics”
•TA231 “TGA Evaluation of Zeolite Catalysts”
•TN6 “Consideration of Subtle Experimental Effects (Simultaneous
TGA-DTA)”
•TN24 “TGA Temperature Calibration Using Curie Point Standards”
•TN40 “Optimizing Stepwise Isothermal Experiments in Hi-Res TGA”
•TS13 “Clarification of Inorganic Decomposition by TG-MS”
•TS39 “Characterization of Polyurethane by TGA and Hi-Res  TGA”
What if I need help?
•TA Tech Tips

http://www.youtube.com/tatechtips
•Call the TA Instruments Hotline

302-427-4163 M-F 8-4:30 Eastern Time
thermalsupport@tainstruments.com
•Visit our Website

http://www.tainstruments.com/
On-site training & e-Training courses
Practical Series Webinars
Thank You
The World Leader in Thermal Analysis,

Rheology, and Microcalorimetry
Appendix A
Calibration Steps
TGA: Certified Calibration Kit
•Certified Temperature Calibration Kit

(P/N 952384.901)
•Secondary Temperature Calibration Materials
(Nickel, Alumel)
•Curie Temperatures traceable to National
Reference Laboratories (NIST, LGC)
•Universal Magnet
•ASTM E1582 test method
•Detailed ISO style calibration instructions
Calibration
•Weight Calibration
Manual – done with pan and known calibration weight
Accessed through TRIOS software Calibrate>Weight
Automatic – done with differential weights from accessory
kit.
Also accessed with Calibrate>Weight
Platinum reference pan has to be on the counter balance.
Calibration - Weight
Choose Weight
Calibration
Calibration – Weight (Auto)
After Calibration is Completed
Enter the mass of the calibration

weight
Simply reload the mass to verify – mass

difference of ~ 0.005%
Calibration - Temperature
•Temperature – Curie Point

•Up to 5 standards may be used
•Experiment will be set up automatically
•Multiple calibrants must be analyzed at once
•Well documented in the help menu
Calibration – Choose Calibrant, Method is
Automatically Generated
Calibration – Temperature
Choose ‘New’
• Choose the appropriate

standard – instrument will
automatically choose the
parameters.
• Be sure to choose the
correct pan number and
type. You can vary the
heating rate, but the
lower and upper
temperature boundaries
are fixed.
• If you choose to send the
run to the ‘Queue’, you
can simply add another
Curie standard as the
next run.
From the ‘Results’

Pane, Choose both
the Alumel and
Nickel Runs
Electromagnet
Switched ON –
Apparent Weight Gain
Curie Point
Choose ‘Calibrations’
and ‘TGA Temperature’
Dialogue Box
Shows Summary
of Calibration –
Choose ‘Save
and Apply’ if Data
is OK
Calibration – Temperature – Completed!
Calibration – Temperature – Verification
•Run Curie samples in the ‘Standard’ mode – not

‘Calibration’
•Analyze Curie Point
•Both standards can be run simultaneously
Calibration – Temperature: Verification
Alumel
Nickel
Calibration – Temperature – Verification
•Protocol is determined by your lab and needs, but there is

no substitute for sound analytical chemistry!
•You simply have to be confident that the data you provide
is correct.
•TA recommends verification on a regular basis.
•Verification is simply running a known standard in the
standard mode and determining the Curie Point for
temperature and …
•Simply placing a known weight on a tared pan and
checking the mass measured by the balance.
•Control charts allow for statistical monitoring of instrument
performance.
•Refer to any analytical chemistry text
How Often Do I Calibrate? – The Case for
Control Charting
• Example:
Laboratory A has TA Instruments come in for a preventive maintenance
visit every January. This visit includes calibration of the temperature and
mass.
No further calibration or verification is performed until September of the
same year when an internal customer questions her data.
A check of the calibrations shows that the instrument is reading 20 °C too
high and the mass 20 mg too low.
When did the calibration change?
With no verification protocol in place, all of the data for the previous 9
months is considered un-reliable. Some protocols require that each client
be notified about the potential discrepancies in their data.
A weekly verification protocol and control chart maintenance would
minimize the amount of suspect data.
Verification of an alumel / nickel calibration takes about 20 minutes.
Verification of the mass calibration using the supplied differential masses
takes less than 10 minutes
•Standard Reference Materials come with a certificate of

measurement that identify:
The best estimate of the known true value of the reference
material.
The uncertainty of the best estimate value. This value
typically represents the 95% confidence limits, (twice the
standard deviation or 2σ), but you must read the certificate
carefully to be sure.
• Standard deviation
and confidence limits
Miller and Miller; Statistics for Analytical

Chemistry, 2nd Edition; Ellis Horwood
Limited
Calibration - Traceable Standards
•Certified – material has been tested using a formal testing

procedure and the signature attests to the validity of the
results
•Traceable – certifies that a documented chain of
comparisons exists connecting the standard to a reference
material maintained by a national metrology laboratory
such as NIST or LGC.
•Should I expect to obtain the same uncertainty values

observed by the certifying agency?
•Not necessarily!
•What should my uncertainty value be? Where do I start?
•A good place is the precision and bias section associated
with the ASTM method for the analysis – in this case
ASTM E1582.
•ASTM Statement:
•How do I determine if my instrument needs calibration?

•One suggestion– maintain control chart of verification
runs. Verification runs are made in the standard mode.
•Accumulate a statistically significant number of runs.
•Decide on appropriate boundaries for the uncertainty
interval.
•What is a statistically significant number of observations?

•The Standard Error of the Mean (SEM) is given by the
function:
σ
SEM =
n
where σ = standard deviation
n = number of observations
0.5 0.5
0.45 0.45
0.4 0.4
0.35 0.35
0.3 0.3
1 / (n)^(1/2)
1 / (n)^(1/2)
0.25 0.25
N=10 N=30
0.2 0.2
0.15 0.15
0.1 0.1
0.05 0.05
0 0
1 10 100
Log n (Number of Measurements)

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Thermogravimetric Analysis (TGA)

Theory and Applications

Presented by Kadine Mohomed, Ph. D

TA Instruments – Waters LLC

Calibration and verification

Kinetics and Activation Energy

Evolve Gas Analysis

•Measurements are used primarily

•Thermal Stability of Materials

All of these are kinetic processes (i.e. there is a rate at which

Deriv. Weight (%/min)

Water weight loss 2

Isothermal Temperature ±1°C ±1°C ±1°C

Sample Weight 1000mg 750 mg 1000 mg

•A TGA must accurately:

Purge gas outlet

Purge gas inlet

Sample pan holder

• The balance operates on a

•A TGA measures the change in mass of a material with respect to

Purge gas and flow rate

•American Society of Testing and Materials, ASTM

•International Organization of Standards, ISO

•Deutsches Institut für Normung/German Institute for Standardization,

•ASTM E 1582 - Standard Practice for Calibration of Temperature

•ASTM E 2040 - Standard Test Method for Mass Scale Calibration of

•ISO 11358 – Thermogravimetry (TG) of Polymers

•The TGA pan should be cleaned prior to calibration procedures. If

•Use high purity reference materials for calibration

•The mass signal generated by a TGA is compared to the mass of a

• This test method calibrates or demonstrates conformity of

Enter the mass of the calibration

Simply reload the mass to verify – mass

Sample Purge 90ml/min of He

Q500 TGA w/ EGA Furnace @ 20°C/min

Balance Purge Flow (mL/min)

•Curie Point Temperature - that temperature where the material loses

•Paramagnetic - a material that is susceptible to attraction by a magnet

•Temperature Calibration points are determined by comparing the

•TA Instruments software allows for up to 5 temperature calibration

Vertical Balance Configuration

•International Confederation for Thermal Analysis and

Curie Temperature Reference Materials

Six curie point standards are available

•Should I expect to obtain the same uncertainty values

•Protocol is determined by your lab and needs, but there is

•Although Calcium Oxalate is not generally accepted as a

•1st Step CaC2O4•H2O (s) CaC2O4 (s) + H2O (g)

•2nd Step CaC2O4 (s) CaCO3 (s) + CO (g)

•3rd Step CaCO3 (s) CaO (s) + CO2 (g)

Overlay of 8 runs, same conditions

[ ––––––– ] Deriv. Weight (%/°C)

Transition 1 Transition 2 Transition 3

Theoretical 12.3 19.2 30.1

Gas Delivery Module – Discovery TGAs

TGA Heat Exchanger

•Mass Flow Controllers

Copper oxalate can be used to detect

Deriv. Weight (%/°C)

10 minute Nitrogen pre-purge

10 minute Nitrogen pre-purge

Deriv. Weight (%/min)

400 450 500 550 20