Thermogravimetric Analysis

(TGA)

TGA: The Technique

Thermogravimetric Analysis (TGA) measures the

amount and rate of change in the weight of a material
as a function of temperature or time in a controlled
atmosphere. Measurements are used primarily to
determine the composition of materials and to predict
their thermal stability at temperatures up to 1000°C.
The technique can characterize materials that exhibit
weight loss or gain due to decomposition, oxidation, or
dehydration.
TGA: What TGA Can Tell You

zComposition of Multicomponent Systems

zThermal Stability of Materials
zOxidative Stability of Materials
zEstimated Lifetime of a Product
zDecomposition Kinetics of Materials
zThe Effect of Reactive or Corrosive Atmospheres
on Materials
zMoisture and Volatiles Content of Materials

TGA: Environment Considerations

zAvoid areas near heater or air conditioner ducts

zAvoid tables with drawers or those near a door

zFor optimum results, use a marble table

TGA: Purge Gas Guidelines

zTGA: Always purge through balance housing with

dry inert gas (i.e. Nitrogen)

zTGA: Only introduce reactive/corrosive gases

through sample area/furnace housing

TGA: Purge Gas Flow Rates

zTGA 2950 Standard zTGA 2050/2950 EGA

Furnace Furnace

100mL/min. total: 100mL/min. total:

40mL/min. balance 10mL/min. balance
60mL/min. furnace 90mL/min. furnace
TGA: Purge Gas

zNitrogen most common

zHelium often provides best baseline

zAir can sometimes improve resolution because of

differences in the oxidative stability (versus
thermal stability) of components

TGA: Cool-down Between Scans

zTGA 2050, 2950

zSelect air cool as method end condition
z2050: Furnace cools to 500°C, then air cools
z2950: Furnace opens, then air cools
TGA: 2050, 2950 - Mass Calibration

zTwo point mass adjustment

z100mg. range (use 100mg. weight)
z1000mg. range (use 1000mg. weight)

zRun TGA weight calibration routine

zFollow screen instructions to tare and mass

calibrate using two calibration weights (if known,
enter exact mass of calibration weights)

TGA: Temperature Calibration

zCurie Point Transition Method

zTGA 2050, 2950

zASTM 1582 - Standard Practice for Calibration of

Temperature Scale for Thermogravimetry
TGA: Temperature Calibration -
Curie Point Transition Method

zParamagnetic - a material that is susceptible to

attraction by a magnet

zCurie Point Temperature - that temperature where

the material loses its magnetic susceptibility
(defined as offset point)

zRequires a magnet and well characterized

transition materials

TGA: Temperature Calibration -

Curie Point Transition Method

Vertical Balance Configuration - TGA 2050/2950

Tare

Sample
%
Offset
Furnace
temp
Attraction of Sample to Magnet
Magnet Results in Initial Weight Gain
TGA: Temperature Calibration
with Magnetic Standards

125

120
Weight (%)

115

110

105

100 361.15°C
NICKEL THEORETICAL 354°C
95
200 250 300 350 400
Temperature (°C)

TGA: Certified Calibration Kit

zCertified Temperature Calibration Kit

(P/N 952384-901)
zSecondary Temperature Calibration Materials
(Nickel, Alumel)
zCurie Temperatures traceable to National
Reference Laboratories (NIST, LGC)
zUniversal Magnet
zASTM E1582 test method
zDetailed ISO style calibration instructions
TGA: Baseline Considerations

zEspecially important for measuring small weight

losses associated with volatilization or small
amounts of residue

zRun clean empty tared pan, over temperature

range of interest @ desired heating rate.

zPlot weight in µg vs. temperature.

TGA: Measuring TGA Baseline Performance

Sample: Baseline File: G:...\Transfer\LEWbsln1.001

Size: 0.0020 mg TGA Operator: Louis Waguespack
Method: Ramp 20 w/ Init Iso Run Date: 7-Dec-1999 14:48

-5

-10
Weight (µg)

-15

-20

-25
0 200 400 600 800 1000
Temperature (°C)
 TGA: Reproducibility of TGA Baseline
Six TGA Baselines @ 20°C/min
2950 TGA w/ Std Furnace and N2 Purge

10

0
Weight (µg)

-10
600.00°C
-20.10µg

-20

600.00°C
-25.04µg
-30
0 200 400 600 800 1000
Temperature (°C)

TGA:Effect of Heating Rate on Baseline

Effect of Heating Rate on 2950 baseline

20° & 50°C/min w/ Std furnace and Nitrogen purge

-5
Weight (µg)

20°C/min
-10

-15

50°C/min

-20

-25
0 200 400 600 800 1000
Temperature (°C)
TGA: Factors Influencing Baseline

zStability of table

zHang down wire condition

zHang down tube condition

zLeveling of TGA

zCleanliness of Furnace

zPurge gas flow rates

TGA: Sample Preparation

zMaximize the surface area of the sample to

improve weight loss resolution and temperature
reproducibility

– Sampleweight
10-20mg for most applications
50-100mg for measuring volatiles

zMost TGA instruments have baseline drift of

+/-0.025mg which is 0.25% of a 10mg sample
TGA: Typical Applications

z Thermal Stability

z Compositional Analysis

z Oxidative Stability

TGA: Evaluation of High Temperature

Polymers

100

80 PI
PVC
WEIGHT PERCENT

HPPE PTFE
PMMA
60

40

20 wt. : 10 mg
prog.: 5°C
atm.,: N
2
0

0 100 200 300 400 500 600 700 800

TEMPERATURE (°C)
 TGA: Block versus Random
Copolymers

100 S - α MS
RANDOM
S - α MS BLOCK
Weight (%)

50 P - α MS

size: 8 mg
prog: 6°C/min
PS
atm: 300 Pa
vacuum

0
0 100 200 300 400 500
Temperature (°C)

TGA: Calcium Oxalate

120 10
[------------] Deriv. Weight (%/min)

8
100 12.3%
WATER 19.2% CO
6
Weight (%)

80
4
60 30.0% CO2
2

40
0

20 -2
0 200 400 600 800 1000
Temperature (°C)
 TGA: EVA COPOLYMERS
[J. Chiu, Appl. Polym. Sym., 2, 25 (1966)]

Acetic Acid
100
23%
WEIGHT PERCENT

390° size : 100 mg

prog : 5°C/min
atm : N 2
50 Vinyl acetate (VA) %= wt loss of acetic
acid x mol wt of VA / mol weight of acetic
acid

86.1
VA(%) = 23% x = 33
60.1
0

200 300 400 500 600 700

TEMPERATURE (°C)

TGA: EPDM Rubber Analysis

2.0
100

1.5
80
Deriv. Weight (%)
Weight (%)

Switch to Air 1.0

60

40 0.5

20 0.0
24.96% Carbon Black + Ash

(5.656mg)
0 -0.5
0 200 400 600 800 1000
Temperature (°C)
TGA: Vegetable Oil Oxidative Stability

137
+

125
Sample Size: 5.18 mg
Temperature: 137°C
Atmosphere: 0 2 at 50 mL/min
WEIGHT CHANGE

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: Standard TGA

zMeans of Enhancing Resolution

zSlower Heating Rate
zReduced Sample Size
zChange Purge Gas
zPin-hole Hermetic Pans
 TGA: Conventional TGA - Calcium
Sulfate Dihydrate (Open Pan)
105 0.6

100

] Deriv. Weight (% / °C)

0.4
95
Weight (%)

90 0.2

85
0.0
80

75 -0.2

[
0 50 100 150 200 250 300 350
Temperature (°C)

TGA: Conventional TGA - Calcium

Sulfate Dihydrate (Pinhole Lid)
105 0.8

100 ] Deriv. Weight (% / °C)

0.6
95
0.4
Weight (%)

90
0.2
85

80 0.0

75 -0.2
[

0 50 100 150 200 250 300 350

Temperature (°C)
TGA: Hi-Res TGA - Alternate Methods

zDynamic (Hi-Res) TGA

zConstant Reaction Rate TGA
zStep Wise Isothermal TGA

TGA: Hi-Res TGA - What is Automated Stepwise

Isothermal TGA?

Heating stops (isothermal) once a certain

operator defined weight loss rate is
exceeded then restarts after this rate falls
below a second operator defined value.
 TGA: Hi-Res TGA - Automated
Stepwise Isothermal
zAdvantages
z Sample held isothermal until transition completed - thus
excellent resolution of overlapping transitions
z Permits careful control of reaction environment
z Available on all TA Instruments TGA's
zDisadvantages
z Difficult method development. May require several scans to
optimize run conditions
z Inappropriate parameter choices may produce artifacts
z Long run time
zUtility
z Routine Analysis of similar samples

TGA: Hi-Res TGA (SWI) - Effect of Entrance

Threshold on Transition Onset

110 108
] TGA Weight (%)
] TGA Weight (%)

98
100

1%/min 88
90 3%/min
4%/min
5%/min 78
80
[

70 68
300 350 400 450 500 550
Temperature (°C)
TGA: Hi-Res TGA (SWI)
Typical SWI Thermal Method

1. Abort next segment if %/min > 5.0

2. Ramp 10°C/min to 1000°C
3. Abort next segment if %/min < 0.5
4. Isothermal 1000 min
5. Repeat 1 until 1000°C

TGA: Hi-Res TGA (SWI) - Effect of

Threshold Ratio on Transition End

1%/min. Exit Threshold, x%/min. Entrance Threshold

50
Exit.TH
40 Ent. TH
TGA Weight (%)

30 1/ 20

1/10
20
1/5
10 1/2

1/1.7
0

-10
350 400 450 500 550
Temperature (°C)
* Note: Curves have been shifted relative to the y-axis to facilitate comparison
TGA: Conventional TGA
Poly(vinyl acetate)

Conventional TGA: ß = 20°C/min.

120 40

] Deriv. Weight (%/min)

100
30
80
Weight (%)

60 20

40 10
20
0
0

[
-20 -10
0 100 200 300 400 500 600 700
Temperature (°C)

TGA: Conventional TGA

Poly(vinyl acetate) - Scouting run

Conventional TGA: ß = 20°C/min.

120 40
P
] Deriv. Weight (%/min)

30
EntranceThreshold:
Entrance Threshold:
1/10(P)
1/10 (P) 20

ExitThreshold:
Exit Threshold:
<1/10 (Ent.TH)
<1/10 (Ent. TH) 10

0
[

-20 -10
0 100 200 300 400 500 600 700
Temperature (°C)
TGA: Hi-Res TGA
SWI - Poly(vinyl acetate)

120 12

100 10

Deriv. Weight (%/min)

80 8
Weight (%)

60 6

40 4

20 2

0 0

-20 -2
0 100 200 300 400 500 600 700
Temperature (°C)

TGA: Poly(vinyl acetate)

Comparison of Modes

110
--- Conventional
90 .... Dynamic
__ Stepwise Isothermal
70
Weight (%)

50

30

10

-10
200 300 400 500 600
Temperature (°C)
 TGA: Comparison of Modes (cont.)

Method development Run time

Mode
(min) (min)
Linear <1 34
Dynamic <1 50
SWI >40 180

TGA: TGA Kinetics -

Wire Insulation Thermal Stability
Wire Insulation Thermal
Stability
100 Conversion
0.5%
1.0%
2.5%

95
WEIGHT LOSS (%)

5%
size: 60mg
atm.: N 2
90 10%

10°C
5°C
85 2.0°C
1.0°C

20%
80
200 250 300 350 400 450 500
Temperature (°C)
TGA: TGA Kinetics -
Heating Rate verses Temperature

460 440 420 400 380 360

10
HEAT RATE (°C/min)

Conversion
5
20
10 5 2.5 1.0 0.5

1
1.4 1.5 1.6
1000/T (K)

TGA: 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)
 ThermoStar + TGA 2950

Mass Spectrometer Basics

• Overview of Mass Spectrometry

• Vacuum Requirements
• Ion Creation
• Ion Filtering
• Ion detection
Mass Spectroscopy

• A gas phase compound is ionized,

accelerated, then filtered according to it’s
mass to charge ratio and detected
• The ionization process typically breaks the
compound into fragments, each with it’s
own mass to charge (m/e) ratio
• The largest m/e detected is called the
parent ion and corresponds to the molecular
weight of the compound.
• The pattern of fragments detected is the
mass spectrum of the compound and can
be used for qualitative identification

Vacuum Requirements

e-

• Filament Longevity +
H H

• Ion Mobility

• Detector Operation

Typical Vacuum ~ 10E-05 Torr

Gas Density ~ 1013 Molecules /m3

(@ 760 T ~ 1025 Molecules /m3 )

The Atomic Model

12 C = 12 A.M.U.

= Electron ~ 0 AMU

= Neutron ~ 1 AMU

= Proton ~ 1AMU

1 AMU = 1.66 X 10 -27 Kg.

Isotope Patterns
Isotope Patterns

Isotope Patterns
 Ionization

Atom Ion
12 C + 1e- 12 C+ + 2e-

Ionization

m/e=6
Double Ionization
12C++ + 3e-
1 e- + 12C

Fragmentation - Ionization

m/e=17

1 e- + 18H2O 1 e- + 17OH 1 e- + 17OH 17OH+ +2 e-

 Some Key Fragment Ions
Mass
Number Key Probable Additional Mass
(m/e) fragments Parent Molecule(s) Number (m/e)

6 C++ CO 12, 28, 29

C++ CO2 12, 28, 44
C++ CxHy 12, 13, 14, 26, 27 etc.
12 C+ CO 28, 29
C+ CO2 28, 29, 44
C+ CxHy 13, 14, 26, 27 etc.
14 N+ N2 28, 29
N+ NH3 15, 16, 17
CH2+ CxHy 12, 13, 26, 27 etc.
CO++ CO 28, 29
16 O+ O2 32, 34
O+ H2O 17, 18
CH4+ CH4 12, 13, 14, 15
NH2+ NH3 14, 15, 17
17 OH+ H2O 16, 18
NH3+ NH3 14, 15, 16
18 H2O+ H2O 16, 17

Typical Ion Formation

Spectrum of CO2 showing the 11 most

intense ions Natural
Abundance's

18O = 0.2%

13C = 1.1%
Closed Ion Source

Neutral Gas
Atom/Molecule
Filaments
Electron

Ion

Ions Out Gas In

10-05 10-04 10-03 10

Pressure
(mBar)

Mass Filter

• Cylindrical Rods.
• Stainless Steel or
Molybdenum.
•Opposite Rods are
Connected Electrically.
•Alignment is Critical
+ - not adjustable.

- +
Mass Filter
y
z

QUADRUPOLE ROD x
ION SOURCE

QUADRUPOLE ROD + + e-
+ + + + + + +
+ +
QUADRUPOLE ROD
SEM
Ii

Selected m/e ion - reaches detector

+
Higher m/e ion - deflected in z-axis
Lower m/e ion - deflected in y-axis

Ion Detectors - Faraday

Ii
e-

I i ~ 10-14....10-9 A
= Selected ion - positive charge

Indestructible Detector but gain = unity.

Cannot detect small ion currents <10-14 Amps.

(Limit depends on electrometer only)
SEM Detector - Chaneltron
MASS FILTER

GAIN ~ 100 106

set by SEM VOLTS

= Selected ion - positive charge- SEM

e- VOLTS ~ - 1500V dc
attracted into SEM by -ve dc volts.

Ii
e-

Can be destroyed by high currents

>10-5 Amps , or by operation at high
pressure. I i ~ 10-14....10-5 A

ThermoStar
Pressure Conditions in the Gas Inlet

Gas In

Transport vacuum

5 x 10-6 10-4 5 5 - 1000 mbar (approx.)

TGA-MS: Capillary Interface

SILICA-LINED CONNECTOR TGA FURNACE

STAINLESS STEEL
CAPILLARY

SAMPLE PAN
HEATING
CONNECTION

1 mm GAP

TO MASS SPECTROMETER
QUADRUPOLE

TEFLON SEAL MOLECULAR LEAK

(SILICON CARBIDE FRIT)

TO SECOND STAGE
OF ROTARY PUMP

Mass-Spec to EGA Furnace

EGA
Furnace
Aluminum Bracket Swagelock Fitting

Silica Capillary
Stainless Steel Sheath
Vespel Drilled Plug
Mass-Spec 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

TGA of Calcium Oxalate

Sample: Calcium Oxalate Monohydrate
Size: 17.6070 mg TGA
Method: RT-->1000°C @ 20°C/min

120 10

8
100

6
Deriv. Weight (%/min)

80
Weight (%)

60

40
0

20 -2
0 200 400 600 800 1000
Temperature (°C) Universal V2.7B TA Instruments
TGA-MS Calcium Oxalate

TGA
derivative weight loss

H2O
m/e=18

CO CO2
m/e=28 m/e=44

0 200 400 600 800

Temperature (°C)

TGA-MS
Sample: 583-35-E
Size: 19.6330 mg TGA

98 4

3
96
Deriv. Weight (%/min)

2
Weight (%)

94

92
0

90 -1
250 252 254 256 258 260 262 264 266
Time (min) Universal V2.7B TA Instruments
 TGA-MS

TGA: Determination of Polymer

Composition (EVA Copolymers)

120
14% Vinyl 14% Vinyl Mass 60
100 Acetate Acetate (Acetic
TGA Weight (%)

40% Vinyl Acid)

Acetate 40% Vinyl
80 Acetate

60
MS Intensity

40 Initial Weight Loss

(Acetic Acid) indicates
Vinyl Acetate Level
20
Mass 56
0 (Hydrocarbon)

0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
 TGA: Smoke Generation in Flame
Retarded Polymers (PVC)

100

80

60
Benzene

MS Intensity
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)