26th John L Waters Symposium - Hyphenated Techniques in Thermal Analysis

HUMAN HEALTH • ENVIRONMENTAL HEALTH

Hyphenated Thermal Analysis TechniquesMarch 8 2015Kevin P MenardPerkinElmer LAS

2

Thermal as incomplete information

Water?

Oil? Organics?

Polymer burns?

Carbon black to CO2?

Inorganic ash?

Structured carbon?

3

What’s missing

Thermal Technique What we measure What’s missing Hyphenated Technique

DSC Changes in heat capacity and enthalpy

Chemical or structural information associated with

changes

NIR, Raman, MS

TGA or STA Loss of weight on heating What comes off in a weight loss FTIR, MS, GC, GCMS, IR-GCMS, ICP-MS,

TMA Size changes on heating Structural changes associatedwith size changes

NIR, Raman, UV

DMA Stiffness changes with heating,Frequency, and Strain

Structural or chemical changes associated with measured

changes

NIR, Raman, UV, MS

4

A quick history…

• 1960s – Use of TGA with MS ◦ Limitations imposed by the vacuum TGA could hold ◦ Gas were collected and manually transferred initially

• 1970s – Development of better systems◦ Transfers lines improved, alterative direct TGMS system tried◦ Other techniques still used “gas bomb”

• 1980s – Wendlandt listed TCD, GC and MS as coupled to TGA◦ Development of FTIRs lead to TG-IR

• 1990s – Provder et al “Hyphenated Techniques in Thermal Analysis”◦ Collected work to date

5

Looking at Hyphenated techniques

• We could divide them:◦ Secondary

measure on the sample

◦ Measurement of evolved gas from the sample

TMA/DMA

Raman NIRUV

6

Secondary Measurements on a Sample

1.0 50 100 150 184.7-0.093

-0.08

-0.06

-0.04

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.203

Index

PC

1 (7

5%)

xxxxxxxx

xxx

xx

xx

x

x

x

x

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xxxxxxxxxxxxxxx

xxxxxxxxxx

xxxxxxxxxxxx

xxxxx

xxx

xxxx

xxx

xxxxx

x

x

x

xx

x

xxxxxxxxxxxxxxx

xxxxxxxxxxx

xxxxxxx

xxxxx

xxxxxxxxxx

xxxxxxxxxxxxx

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Bad material Good material

Amorphous solid

Melt

Crystalline polymorph II

Crystalline polymorph III

100 150 20050

Heat flow

Temperature /oC

7

Chemo-rheology

BisGMA TEGDMA

0.0E+00

5.0E+06

1.0E+07

1.5E+07

2.0E+07

2.5E+07

3.0E+07

3.5E+07

4.0E+07

0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%Conversion

Mod

ulus

(Pa)

Loss Modulus (Pa)

Storage Modulus (Pa)

8

Evolved Gas Analysis

• Probably 75-85% of the hyphenated techniques

• To quote a colleague at DuPont:“TGA on its own is of limited utility”

• What comes when off helps define what is happening.

Water?Oil? Organics?

Polymer burns?

Carbon black to CO2?

9

TG-IR TG-MS TG-GCMS TG-IR-GCMSFunctional group analysis

Limited to strong bands

Lots of Vapor Phase librariesTG-IR are being to be made

Real time analysisQualitative

Sensitivity LimitedDifficulties in mixture analysisCan be swamped by H2O or

and CO2

Non-destructive on vaporLow cost option

Mass ions/Fragment analysisIsotope analysis

Widely Applicable

Libraries Available but more limited

Real Time AnalysisQuantitative

Highly SensitiveHigh mass washoverAMU range concerns

DestructiveMore expensive as AMU

range increases

Resolves overlapping eventsOptions for alternative Detectors

Excellent GC libraries

Not real timeQuantitative & Qualitative

Extremely SensitiveColumns can be O2 sensitive

DestructiveComplex to operate

Resolves overlapping eventsIR allows real time analysis

Need both GCMS and IR libraries

IR allows real time analysisMostly Qualitative at this time

Senstivitivity variesAdvantages and Disadvantages of both

Destructive on vapor in GCMSVery complex to operate

TG-IR

10

TG-IR Decomposition of a TPE

11

Combined

-0.01

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

Abso

rban

ce

1000 1500 2000 2500 3000 3500 4000 TFS

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

Abso

rban

ce

1000 1500 2000 2500 3000 3500 4000

-0.04

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.26

0.28

0.30

0.32

0.34

0.36

0.38

Abso

rban

ce

1000 1500 2000 2500 3000 3500 4000

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.26

0.28

Abso

rban

ce

1000 1500 2000 2500 3000 3500 4000

12

Organic contaminated soil

Gram-Schmidt

Weight

Derivative weight

100 200 300 400 500 600 700

°C

13

Soil (con’t)

Gram-Schmidt thermogram

Alkane C-H

Biodiesel alkene C-H

Carbon dioxide

Water

200 400 600

600Temperature (°C)

Abs

14

TG-IR TG-MS TG-GCMS TG-IR-GCMSFunctional group analysis

Limited to strong bands

Lots of Vapor Phase librariesTG-IR are being to be made

Real time analysisQualitative

Sensitivity LimitedDifficulties in mixture analysisCan be swamped by H2O or

and CO2

Non-destructive on vaporLow cost option

Mass ions/Fragment analysisIsotope analysis

Widely Applicable

Libraries Available

Real Time AnalysisQuantitative

Highly SensitiveHigh mass washoverAMU range concerns

DestructiveMore expensive as AMU

range increases

Resolves overlapping eventsOptions for alternative Detectors

Excellent GC libraries

Not real timeQuantitative & Qualitative

Extremely SensitiveColumns can be O2 sensitive

DestructiveComplex to operate

Resolves overlapping eventsIR allows real time analysis

Need both GCMS and IR libraries

IR allows real time analysisMostly Qualitative at this time

Senstivitivity variesAdvantages and Disadvantages of both

Destructive on vapor in GCMSVery complex to operate

TG-MS

15

TG- MS for Residual Solvents in Pharmaceuticals

16

TG-MS for Polymer Identification

Acetic Acid

17

TG-IR TG-MS TG-GCMS TG-IR-GCMSFunctional group analysis

Limited to strong bands

Lots of Vapor Phase librariesTG-IR are being to be made

Real time analysisQualitative

Sensitivity LimitedDifficulties in mixture analysisCan be swamped by H2O or

and CO2

Non-destructive on vaporLow cost option

Mass ions/Fragment analysisIsotope analysis

Widely Applicable

Libraries Available

Real Time AnalysisQuantitative

Highly SensitiveHigh mass washoverAMU range concerns

DestructiveMore expensive as AMU

range increases

Resolves overlapping eventsOptions for alternative Detectors

Excellent GC libraries

Not real timeQuantitative & Qualitative

Extremely SensitiveColumns can be O2 sensitive

DestructiveComplex to operate

Resolves overlapping eventsIR allows real time analysis

Need both GCMS and IR libraries

IR allows real time analysisMostly Qualitative at this time

Senstivitivity variesAdvantages and Disadvantages of both

Destructive on vapor in GCMSVery complex to operate

TG-GCMS

18

TG-GCMS for Biofuel Characterization of Switch grass

19

Coffee beans stored in plastic

(replib) Caffeine0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

0

50

100

27

42

55

6782

94

109

137 165

194

N

N

N

N

O

O

(replib ) Diethyl Phthalate0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

0

50

100

29

39 5065 76 93 105

121132

149

177

222

O

O

O

O

20

TG-GCMS - Natural Rubber Blends

A series of Natural Rubbers blended with SBR Total signal from the evolved gas from the TGA

21

TG-GCMS - Natural Rubber Blends (con’t)

y = 0.2055x - 0.0442R² = 0.9979

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0 5 10 15 20 25

%SB

R

Styrene Peak Area (x 106)

Styrene Peak Area vs. %SBR

(mainlib) Styrene40 50 60 70 80 90 100 110 120

0

50

100

40

51

63 74

78

89 98

104

22

TG-IR-GCMS

TG-IR TG-MS TG-GCMS TG-IR-GCMSFunctional group analysis

Limited to strong bands

Lots of Vapor Phase librariesTG-IR are being to be made

Real time analysisQualitative

Sensitivity LimitedDifficulties in mixture analysisCan be swamped by H2O or

and CO2

Non-destructive on vaporLow cost option

Mass ions/Fragment analysisIsotope analysis

Widely Applicable

Libraries Available

Real Time AnalysisQuantitative

Highly SensitiveHigh mass washoverAMU range concerns

DestructiveMore expensive as AMU

range increases

Resolves overlapping eventsOptions for alternative Detectors

Excellent GC libraries

Not real timeQuantitative & Qualitative

Extremely SensitiveColumns can be O2 sensitive

DestructiveComplex to operate

Resolves overlapping eventsIR allows real time analysis

Need both GCMS and IR libraries

IR allows real time analysisMostly Qualitative at this time

Senstivitivity variesAdvantages and Disadvantages of both

Destructive on vapor in GCMSVery complex to operate

23

TG-IR-GCMS

24

Aqueous Pigment

,

5.82 6.32 6.82 7.32 7.82 8.32 8.82 9.32 9.82 10.32 10.82 11.32 11.82 12.32 12.82 13.32 13.82 14.32 14.82 15.32 10

100

%

jcolors11.36

15.7315.47

25

Thanks to:

• Veritas Testing & Consulting for the TG-IR data on TPE

• Dr. J. Stansbury of U. Colorado Dental School for UV-DMA-NIR

• PerkinElmer Staff:◦ Ben Perston (Soil – Diesel)◦ Tiffany Kang (Rubber)◦ Richard Spragg (DSC-Raman)◦ Maria Garavaglia (Dye)◦ Bill Goodman (Coffee Beans)

• Some References:◦ R. Schwenker Jr. and P. Garn,

Thermal Analysis, Academic Press, 1969

◦ W. Wendlandt, Thermal Analysis #rd Edition, John Wiley & Sons, 1986

◦ T. Provder et al, Hyphenated Techniques in Polymer Characterization, ACS Symposium Series 581, ACS Publishing, 1994

◦ W. Groenewund, Characterization of Polymers by Thermal Analysis, Elsevier Science, 2001.