26th John L Waters Symposium - Hyphenated Techniques in Thermal Analysis
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Hyphenated thermal analysis system allow a greater understanding of materials and processes. This talk from the John L Waters Symposium at PittCon 2015 discusses the history and current state of the techniques
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26th John L Waters Symposium - Hyphenated Techniques in Thermal Analysis
- 1. HUMAN HEALTH • ENVIRONMENTAL HEALTH Hyphenated Thermal Analysis Techniques March 8 2015 Kevin P Menard PerkinElmer LAS
- 2. 2 Thermal as incomplete information Water? Oil? Organics? Polymer burns? Carbon black to CO2? Inorganic ash? Structured carbon?
- 3. 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 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. 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. 5 Looking 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. 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 PC1(75%) xxxx x x xx x x x x x x x x x x x x x xx xxxxxxxxxxxxxxx x x x x x x xx xxxxx x xx x x x xx x xxx xxxxxxxxxxxxxx x x x xxx x x x x xx x x x x x x x x x xxxxxxxxx x xxx xx x xxx x x xx xxx xxxx xxx xx xxx xxxxxx xxxx xxxx xxxxx xxx x xx xx x x x xx Bad material Good material Amorphous solid Melt Crystalline polymorph II Crystalline polymorph III 100 150 20050 Heat flow Temperature /oC
- 7. 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 Modulus(Pa) Loss Modulus (Pa) Storage Modulus (Pa)
- 8. 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. 9 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
- 10. 10 TG-IR Decomposition of a TPE
- 12. 12 Organic contaminated soil Gram-Schmidt Weight Derivative weight 100 200 300 400 500 600 700 °C
- 13. 13 Soil (con’t) Gram-Schmidt thermogram Alkane C-H Biodiesel alkene C-H Carbon dioxide Water 200 400 600 600 Temperature (°C) Abs
- 14. 14 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
- 15. 15 TG- MS for Residual Solvents in Pharmaceuticals
- 16. 16 TG-MS for Polymer Identification Acetic Acid
- 17. 17 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
- 18. 18 TG-GCMS for Biofuel Characterization of Switch grass
- 19. 19 Coffee beans stored in plastic (replib) Caffeine 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 N N O O (replib) Diethyl Phthalate 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 0 50 100 29 39 50 65 76 93 105 121 132 149 177 222 O O O O
- 20. 20 TG-GCMS - Natural Rubber Blends A series of Natural Rubbers blended with SBR Total signal from the evolved gas from the TGA
- 21. 21 TG-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 106) Styrene Peak Area vs. %SBR (mainlib) Styrene 40 50 60 70 80 90 100 110 120 0 50 100 40 51 63 74 78 89 98 104
- 22. 22 TG-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
- 23. 23 TG-IR-GCMS
- 24. 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 1 0 100 % jcolors 11.36 15.7315.47
- 25. 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.