Post on 21-Jul-2015
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
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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
xxxxxxxxx
Bad material Good material
Amorphous solid
Melt
Crystalline polymorph II
Crystalline polymorph III
100 150 20050
Heat flow
Temperature /oC
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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)
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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
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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
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Soil (con’t)
Gram-Schmidt thermogram
Alkane C-H
Biodiesel alkene C-H
Carbon dioxide
Water
200 400 600
600Temperature (°C)
Abs
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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
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
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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
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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
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.