Hyphenated techniques in thermal analysis acs

Slides from my ACS webinar on hyphenated or coupled techniques in thermal analysis.

1. HUMAN HEALTH • ENVIRONMENTAL HEALTH
© 2014 PerkinElmer
HUMAN HEALTH • ENVIRONMENTAL HEALTH
Hyphenated Techniques in Thermal
Analysis
Kevin P Menard PerkinElmer LAS

2. 2Thermal as incomplete information
Water?
Oil? Organics?
Polymer burns?
Carbon black to CO2?
Inorganic ash?
Structured carbon?

3. 3What’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 associated
with 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. 4A 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. 5Looking at Hyphenated techniques
•We could divide
them:
◦Secondary
measure on the
sample
◦Measurement of
evolved gas
from the sample
TMA/
DMA
Raman
NIR
UV

6. 6General Concerns for Any Hyphenated Technique

7. 7Secondary 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 (75%)
x
x
xx
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
xx
xxxx
xxxxxxx
xx
xx
x
x
x
x
x
x
x
x
xx
xx
x
x
x
x
x
x
x
x
x
x
xxx
x
xx
xxx
x
xx
xxx
x
x
x
x
x
xxx
x
x
x
x
xx
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
xx
x
x
x
xx
xx
x
xxx
x
x
xx
x
xx
x
xxx
xx
x
xx
xx
x
xx
xxx
x
xx
x
x
x
x
x
x
xxx
x
x
x
xx
x
xx
xx
x
x
x
xx
Bad materialGood material
Amorphous solid
Melt
Crystalline polymorph II
Crystalline polymorph III
100 150 200
50
Heat flow
Temperature /
o
C

8. 8Chemo-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
Modulus (Pa)
Loss Modulus (Pa) Storage Modulus (Pa)

9. 9Evolved 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?

10. 10Evolved Gas Concerns

11. 11
TG-IR TG-MS TG-GCMS TG-IR-GCMS
Functional group analysis
Limited to strong bands
Lots of Vapor Phase libraries
TG-IR are being to be made
Real time analysis
Qualitative
Sensitivity Limited
Difficulties in mixture analysis
Can be swamped by H2O or
and CO2
Non-destructive on vapor
Low cost option
Mass ions/Fragment analysis
Isotope analysis
Widely Applicable
Libraries Available but more
limited
Real Time Analysis
Quantitative
Highly Sensitive
High mass washover
AMU range concerns
Destructive
More expensive as AMU
range increases
Resolves overlapping events
Options for alternative
Detectors
Excellent GC libraries
Not real time
Quantitative & Qualitative
Extremely Sensitive
Columns can be O2 sensitive
Destructive
Complex to operate
Resolves overlapping events
IR allows real time analysis
Need both GCMS and IR
libraries
IR allows real time analysis
Mostly Qualitative at this time
Senstivitivity varies
Advantages and
Disadvantages of both
Destructive on vapor in GCMS
Very complex to operate
TG-IR

12. 12TG-IR Decomposition of a TPE

13. 13Combined
-0.01 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10
Absorbance
100 0
150 0
200 0
250 0
300 0
350 0
400 0
TF S
-0.02 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0
.20
Ab s o r b a n c e
100 0
150 0
200 0
250 0
300 0
350 0
400 0
-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 0.360.38
Absorbance
100 0
150 0
200 0
250 0
300 0
350 0
400 0
-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
Absorbance
100 0
150 0
200 0
250 0
300 0
350 0
400 0

14. 14Organic contaminated soil
Gram-Schmidt
Weight
Derivative weight
100 200 300 400 500 600 700
°C

15. 15Soil (con’t)
Gram-Schmid
tthermogram
Alkane C-H
Biodiesel alkene
C-H
Carbon dioxide
Water
200 400
600600
Temperature (°C)
Abs

16. 16
TG-IR TG-MS TG-GCMS TG-IR-GCMS
Functional group analysis
Limited to strong bands
Lots of Vapor Phase libraries
TG-IR are being to be made
Real time analysis
Qualitative
Sensitivity Limited
Difficulties in mixture analysis
Can be swamped by H2O or
and CO2
Non-destructive on vapor
Low cost option
Mass ions/Fragment analysis
Isotope analysis
Widely Applicable
Libraries Available
Real Time Analysis
Quantitative
Highly Sensitive
High mass washover
AMU range concerns
Destructive
More expensive as AMU
range increases
Resolves overlapping events
Options for alternative
Detectors
Excellent GC libraries
Not real time
Quantitative & Qualitative
Extremely Sensitive
Columns can be O2 sensitive
Destructive
Complex to operate
Resolves overlapping events
IR allows real time analysis
Need both GCMS and IR
libraries
IR allows real time analysis
Mostly Qualitative at this time
Senstivitivity varies
Advantages and
Disadvantages of both
Destructive on vapor in GCMS
Very complex to operate
TG-MS

17. 17TG- MS for Residual Solvents in Pharmaceuticals

18. 18TG-MS for Polymer Identification
Acetic Acid

19. 19
TG-IR TG-MS TG-GCMS TG-IR-GCMS
Functional group analysis
Limited to strong bands
Lots of Vapor Phase libraries
TG-IR are being to be made
Real time analysis
Qualitative
Sensitivity Limited
Difficulties in mixture analysis
Can be swamped by H2O or
and CO2
Non-destructive on vapor
Low cost option
Mass ions/Fragment analysis
Isotope analysis
Widely Applicable
Libraries Available
Real Time Analysis
Quantitative
Highly Sensitive
High mass washover
AMU range concerns
Destructive
More expensive as AMU
range increases
Resolves overlapping events
Options for alternative
Detectors
Excellent GC libraries
Not real time
Quantitative & Qualitative
Extremely Sensitive
Columns can be O2 sensitive
Destructive
Complex to operate
Resolves overlapping events
IR allows real time analysis
Need both GCMS and IR
libraries
IR allows real time analysis
Mostly Qualitative at this time
Senstivitivity varies
Advantages and
Disadvantages of both
Destructive on vapor in GCMS
Very complex to operate
TG-GCMS

20. 20TG-GCMS for Biofuel Characterization of Switch grass

21. 21Coffee beans stored in plastic
(rep lib ) Ca ffeine
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
0
50
100
27
42
55
67
82
94
109
137
165
194
N
N
NN
O
O
(rep lib ) Diethyl Phtha la te
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
0
50
100
29
39
50
65
76
93105
121
132
149
177
222
O
OO
O

22. 22TG-GCMS - Natural Rubber Blends A series of Natural Rubbers blended with SBR
Total signal from the evolved gas from the TGA

23. 23TG-GCMS - Natural Rubber Blends (con’t)
y = 0.2055x - 0.0442
R² = 0.9979
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 5 10 15 20 25
%SBR
Styrene Peak Area (x 10
6
)
Styrene Peak Area vs. %SBR
(
mainlib
)
St
y
rene
40
50
60
70
80
90
100
110
120
0
50
100
40
51
63
74
78
89
98
104

24. 24TG-IR-GCMS
TG-IR TG-MS TG-GCMS TG-IR-GCMS
Functional group analysis
Limited to strong bands
Lots of Vapor Phase libraries
TG-IR are being to be made
Real time analysis
Qualitative
Sensitivity Limited
Difficulties in mixture analysis
Can be swamped by H2O or
and CO2
Non-destructive on vapor
Low cost option
Mass ions/Fragment analysis
Isotope analysis
Widely Applicable
Libraries Available
Real Time Analysis
Quantitative
Highly Sensitive
High mass washover
AMU range concerns
Destructive
More expensive as AMU
range increases
Resolves overlapping events
Options for alternative
Detectors
Excellent GC libraries
Not real time
Quantitative & Qualitative
Extremely Sensitive
Columns can be O2 sensitive
Destructive
Complex to operate
Resolves overlapping events
IR allows real time analysis
Need both GCMS and IR
libraries
IR allows real time analysis
Mostly Qualitative at this time
Senstivitivity varies
Advantages and
Disadvantages of both
Destructive on vapor in GCMS
Very complex to operate

25. 25TG-IR-GCMS

26. 26Aqueous 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 1
0
100
%
jcolors
11.36
15.73
15.47

27. 27Thanks 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.