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 1000C. 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 100mL/min. total: 40mL/min. balance 60mL/min. furnace

Furnace 100mL/min. total: 10mL/min. balance 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 500C, 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 % Furnace Magnet Attraction of Sample to Magnet Results in Initial Weight Gain Offset temp

TGA: Temperature Calibration with Magnetic Standards

125 120 Weight (%) 115 110 105 100 95
NICKEL THEORETICAL 354C 361.15C

200

250 300 Temperature (C)

350

400

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 g vs. temperature.

TGA: Measuring TGA Baseline Performance

Sample: Baseline Size: 0.0020 mg Method: Ramp 20 w/ Init Iso 0

TGA

File: G:...\Transfer\LEWbsln1.001 Operator: Louis Waguespack Run Date: 7-Dec-1999 14:48

-5

-10

Weight (g)

-15

-20

TGA: Reproducibility of TGA Baseline

Six TGA Baselines @ 20C/min 2950 TGA w/ Std Furnace and N2 Purge
10

Weight (g)

-10

600.00C -20.10g

-20

600.00C -25.04g
-30 0 200 400 600 800 1000

Temperature (C)

TGA:Effect of Heating Rate on Baseline

Effect of Heating Rate on 2950 baseline 20 & 50C/min w/ Std furnace and Nitrogen purge
5

-5

Weight (g)

20C/min
-10

-15

50C/min
-20

-25

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

Sample

weight 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

Thermal Stability Compositional Analysis Oxidative Stability

TGA: Evaluation of High Temperature Polymers

100 80 WEIGHT PERCENT
PVC PMMA HPPE PTFE

PI

60 40 20 0 0
wt. : 10 mg prog.: 5C atm.,: N
2

100

200

300 400 500 600 TEMPERATURE (C)

700

800

TGA: Block versus Random Copolymers

100
S - MS BLOCK S - MS RANDOM

Weight (%)

50
size: prog: atm: 8 mg 6C/min 300 Pa vacuum

P - MS

PS

100

200 300 Temperature (C)

400

500

TGA: Calcium Oxalate

120 100 Weight (%) 80 60 40 20 0 200 400 600 Temperature (C) 800
12.3% WATER

10 8
19.2% CO

6 4
30.0% CO2

2 0

-2 1000

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

TGA: EVA COPOLYMERS

[J. Chiu, Appl. Polym. Sym., 2, 25 (1966)]
Acetic Acid

100
23%

WEIGHT PERCENT

390

50

Vinyl acetate (VA) %= wt loss of acetic acid x mol wt of VA / mol weight of acetic acid

size : 100 mg prog : 5C/min atm : N 2

VA(%) = 23% x
0 200

86.1 = 33 60.1

300 400 500 TEMPERATURE (C)

600

700

TGA: EPDM Rubber Analysis

100 2.0

80 Weight (%)
Switch to Air

1.5 Deriv. Weight (%)

60

1.0

40

0.5

20
24.96% Carbon Black + Ash (5.656mg)

0.0

-0.5

TGA: Vegetable Oil Oxidative Stability

137 125
0.05

WEIGHT CHANGE

Sample Size: Temperature: Atmosphere:

5.18 mg 137C 0 2 at 50 mL/min

100 75 TEMP (C)

02 57 MINUTES FIRST DEVIATION

50 25

0 10

20

30

40 50 60 TIME (Min.)

70

80

90

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)

105 100 0.4 95 Weight (%) 90 85 0.0 80 75 0 50 100 150 200 250 Temperature (C) 300 350 -0.2 0.2 ] Deriv. Weight (% / C) [ 0.6

TGA: Conventional TGA - Calcium Sulfate Dihydrate (Pinhole Lid)

105 100 95 Weight (%) 90 85 80 75 0 50 100 150 200 250 300 0.2 0.0 -0.2 350 0.8 0.6 0.4 ] Deriv. Weight (% / 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 ] TGA Weight (%) 108 98
1%/min 3%/min 4%/min 5%/min

100

90

88

80 [

78 [

70 300

350

400

450

500

68 550

] TGA Weight (%)

TGA: Hi-Res TGA (SWI) Typical SWI Thermal Method

1. 2. 3. 4. 5. Abort next segment if %/min > 5.0 Ramp 10C/min to 1000C Abort next segment if %/min < 0.5 Isothermal 1000 min Repeat 1 until 1000C

TGA: Hi-Res TGA (SWI) - Effect of Threshold Ratio on Transition End

1%/min. Exit Threshold, x%/min. Entrance Threshold
50 40 TGA Weight (%) 30 20 10 0 -10

Exit.TH Ent. TH
1/ 20 1/10 1/5 1/2 1/1.7

TGA: Conventional TGA Poly(vinyl acetate)

Conventional TGA: = 20C/min.
120 100 80 Weight (%) 60 40 20 0 -20 0 100 200 300 400 500 Temperature (C) 600 700 0 -10 [ 20 10 40 30 ] Deriv. Weight (%/min) [ -20 0 100 200 300 400 500 600 700 -10 ] Deriv. Weight (%/min)

TGA: Conventional TGA Poly(vinyl acetate) - Scouting run

Conventional TGA: = 20C/min.
120 40

P
30

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

20 10 0

TGA: Hi-Res TGA SWI - Poly(vinyl acetate)

120 100 80 Weight (%) 60 40 20 0 -20 0 100 200 300 400 500 Temperature (C) 600 700

12 10 8 6 4 2 0 -2 Deriv. Weight (%/min)

TGA: Poly(vinyl acetate) Comparison of Modes

110 90 70 50 30 10 -10

--- Conventional .... Dynamic __ Stepwise Isothermal

Weight (%)

200

300

400 Temperature (C)

500

600

TGA: Comparison of Modes (cont.)

Mode Linear Dynamic SWI

Method development (min) <1 <1 >40

Run time (min) 34 50 180

TGA: TGA Kinetics Wire Insulation Thermal Stability

Wire Insulation Thermal Stability
100
0.5% 1.0% 2.5% 5%

Conversion

WEIGHT LOSS (%)

95
size: 60mg atm.: N 2

90

10%

85

10C 5C 2.0C 1.0C 20%

80

Heating Rate verses Temperature

460 10 440 420 400 380 360

HEAT RATE (C/min)

Conversion 20 10 5 2.5 1.0 0.5

1 1.4 1000/T (K) 1.5 1.6

TGA: TGA Kinetics Estimated Lifetime

260 280 300 320 340 360 1 century 1 decade 1 yr. 1 mo. 1 week 100 1 day 10 1.9 1.8 1.7 1.6 1.5 ESTIMATED LIFE
TEMPERATURE (C)

1000000 100000 10000 1000

ESTIMATED LIFE (hr.)

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 its mass to charge ratio and detected The ionization process typically breaks the compound into fragments, each with its 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
12

Ion
12

C + 1e-

C+ + 2e-

Ionization
Double Ionization
1 e- +
12C

m/e=6
12C++

+ 3e-

Fragmentation - Ionization
m/e=17 1 e- +
18H2O

1 e- +

17OH

1 e- +

17OH

17OH+

+2 e-

Some Key Fragment Ions

Mass Number (m/e)
6 12 14

Key fragments
C++ C++ C++ C+ C+ C+ N+ N+ CH2+ CO++ O+ O+ CH4+ NH2+ OH+ NH3+ H2O+

Probable Parent Molecule(s)

CO CO2 CxHy CO CO2 CxHy N2 NH3 CxHy CO O2 H2O CH4 NH3 H2O NH3 H2O

Additional Mass Number (m/e)

12, 28, 29 12, 28, 44 12, 13, 14, 26, 27 etc. 28, 29 28, 29, 44 13, 14, 26, 27 etc. 28, 29 15, 16, 17 12, 13, 26, 27 etc. 28, 29 32, 34 17, 18 12, 13, 14, 15 14, 15, 17 16, 18 14, 15, 16 16, 17

16

17 18

Typical Ion Formation

Spectrum of CO2 showing the 11 most intense ions

Natural Abundance's
18O

= 0.2% = 1.1%

13C

Closed Ion Source

Neutral Gas Atom/Molecule Electron Ion

Filaments

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 x
+

QUADRUPOLE ROD ION SOURCE

+ + + + +

QUADRUPOLE ROD + + + + + QUADRUPOLE ROD

e-

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 chargeattracted into SEM by -ve dc volts.

e-

SEM VOLTS ~ - 1500V dc

Ii
eCan 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 - 1000 m bar (approx.)

TGA-MS: Capillary Interface

SILICA-LINED STAINLESS STEEL CAPILLARY

CONNECTOR

TGA FURNACE

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

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 Method: RT-->1000C @ 20C/min 120

TGA
10

8 100

80

4 60 2

40 0

Deriv. Weight (%/min)

Weight (%)

TGA-MS Calcium Oxalate

TGA derivative weight loss

H2O m/e=18 CO m/e=28 CO2 m/e=44

200

400

600

800

Temperature (C)

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

TGA
4

98

3 96

Weight (%)

2 94 1

92 0

Deriv. Weight (%/min)

TGA-MS

TGA: Determination of Polymer Composition (EVA Copolymers)

120 TGA Weight (%) 100 80 60 40 20 0 0 100 200 300 400 500 600 Temperature (C)
Initial Weight Loss (Acetic Acid) indicates Vinyl Acetate Level 40% Vinyl Acetate 14% Vinyl Acetate 14% Vinyl Acetate 40% Vinyl Acetate Mass 60 (Acetic Acid)

MS Intensity

Mass 56 (Hydrocarbon)

100 200 300 400 500 600 Temperature (C)

TGA: Smoke Generation in Flame Retarded Polymers (PVC)

100 80 60
PVC Benzene (78 amu)

MS Intensity

TGA Weight (%)

40 20 0

PVC + MoO 3

100

200 300 400 Temperature (C)

500

100

200 300 400 Temperature (C)

500