Thermal Characterization of Nanocrystalline Cellulose For Polymer ...
Thermal Characterization of Nanocrystalline Cellulose For Polymer Nanocomposite Applications Andrew C. Finkle, C. Ravindra Reddy, Leonardo Simon University of Waterloo 200 University Av. W., Waterloo, ON, Canada
Outline
2
Introduction: Motivation Materials: Nanocrystalline Cellulose sources Method: TGA, Flynn-Wall-Ozawa, Moisture Results: Onset of Degradation, EA, %MC Conclusion
Introduction
Cellulose as a bio-based polymer reinforcement
Interest to replace metal and glass with plastic High temperature polymer processing will cause thermal degradation of cellulose
3
sustainable, recyclable, and non-toxic
colour change, odour, reduction in strength and long-term stability
Quantify thermal stability of cellulose
Materials: Cellulose Sources Alberta Innovates – Technology Futures 1. Nanocrystalline Cellulose (NCC-Alb) Nanocrystalline Cellulose As received: small off-white flakes (~1mm) water soluble at few wt% 100nm fibers FP Innovations 2. Nanocrystalline Cellulose (NCC-FP) Nanocrystalline Cellulose from Canadian wood sources As received: low density translucent flakes water soluble at a few wt% 200nm x 10nm fibers2
4
J. RETTENMAIER & SÖHNE GMBH+CO.KG 3. UltraFine Cellulose 100 (UFC-100)
Microcrystalline cellulose As received: small off-white flakes (~1mm)
water dispersible at few wt%
~4.5um microfibers
4. NanoDisperse Cellulose (MF 40-10)
Nano/Microcrystalline Cellulose
As received: dispersion, white paste
~1-5um microfibers
Methods Thermogravimetric Analysis (TGA)
Weight change of cellulose as a function of a preprogrammed heating profile Thermal degradation is proportional to the conversion of cellulose from solid to gaseous products Temperature: 35-600ºC Heating rates: 5, 10, 20, 30, 40ºC per minute Gas atmosphere: Air and N2
5
Methods Flynn-Wall-Ozawa3
6
Determine activation energy as a kinetic parameter of thermal degradation EA determined from plot of log β versus -1/RT at a constant conversion (over multiple heating rates) and will result in a line with a slope of 0.4567*EA Focus on initial section of conversion (0.98 EA lines nearly parallel and constant, confirming that the activation energies do not depend on previous conversion (except NCC-Alb)
NCC-FP > MF 40-10 > UFC-100 > NCC-Alb varied from 204.7 to 111.9 kJ/mol between the NCC-FP and NCC-Alb inconsistency and lower magnitude for the NCC-Alb source can be associated to inclusions of lignin, hemi-cellulose, or some other impurity
Results: Moisture Content
Each cellulose source was tested for moisture content on four random days
17
The standard deviations are low as the %MC did not fluctuate too dramatically during the testing.
Conclusions
EA for EA for EA for EA for
NCC-Alb were 122 kJ/mol and 130 kJ/mol in air and nitrogen respectively NCC-FP were were higher at 184 and 202 kJ/mol for air and nitrogen UFC-100 were were higher at 136 and 145 kJ/mol for air and nitrogen MF 40-10 were were higher at 152 and 166 kJ/mol for air and nitrogen
NCC-FP and UFC-100 sample contained less impurities than the other sources
UFC-100 had the highest Onset of Degradation followed by NCC-FP, MF 40-10, and NCC-Alb
EA for NCC-Alb appeared more dependent on conversion than the other cellulose sources
18
EA and Onset of Degradation temperature was calculated for NCC-Alb, NCC-FP, UFC100 and MF 40-10 using Flynn-Wall-Ozawa method
The calculated EA and onset temperatures can be used to model and predict mass loss during a specific processing temperature profile as well as screening for the best candidate to use in a polymer nanocomposite5 The moisture content for NCC-Alb is approximately 4.9%; for NCC-FP it is slightly higher at 6.4%; and UFC-100 and MF 40-10 had %MC of 6.3% and 5.7% respectively
Acknowledgements The authors would also like to thank FP Innovations, Alberta Innovates, and JRS Inc. for donating the cellulose samples; and acknowledge financial support from the Natural Science and Engineering Council of Canada (Discovery Grant) and the Ontario Ministry of Research and Innovation (The Ontario BioCar Initiative).
References M.A. Hubbe, O.J. Rojas, L.A. Lucia, and M. Sain, “Cellulosic nanocomposites: A Review,” BioResources, vol. 3, 2008, pp. 929-980. FP Innovations. 2008. Nanocrystalline Cellulose – ‘Green’ Nanoparticles. Brochure. Pointe-Claire, PQ. JRS Inc., “UFC-100 Material Specification Sheet,” 2010. JRS Inc., “MF 40-10 Material Specification Sheet,” 2010. T. Ozawa, “Kinetic analysis of derivative curves in thermal analysis,” Journal of Thermal Analysis, vol. 2, Sep. 1970, pp. 301-324. M. Golbabaie, “Characterization of Ontario Crop Fibres for Use in Biocomposites (Wheat and Soybean),” University of Guelph. MSc Thesis. 2008. 7. D.K. Misra. In: F. Hamilton, B. Leopold and M.J. Kocurek, Editors, (Version 5 Edition ed.),Pulp and Paper Manufacture Vol. 3, Joint Textbook Committee of the Paper Industry TAPPI-CPPA, Montreal, Canada (1987), pp. 82–93 Secondary Fibers and Nonwood Pulping .
1. 2. 3. 4. 5. 6.
19
Thank you PRESENTED BY
Andrew C. Finkle MASc ChemEng (Nano)
University of Waterloo [email protected]
Please remember to turn in your evaluation sheet...
Outline
2
Introduction: Motivation Materials: Nanocrystalline Cellulose sources Method: TGA, Flynn-Wall-Ozawa, Moisture Results: Onset of Degradation, EA, %MC Conclusion
Introduction
Cellulose as a bio-based polymer reinforcement
Interest to replace metal and glass with plastic High temperature polymer processing will cause thermal degradation of cellulose
3
sustainable, recyclable, and non-toxic
colour change, odour, reduction in strength and long-term stability
Quantify thermal stability of cellulose
Materials: Cellulose Sources Alberta Innovates – Technology Futures 1. Nanocrystalline Cellulose (NCC-Alb) Nanocrystalline Cellulose As received: small off-white flakes (~1mm) water soluble at few wt% 100nm fibers FP Innovations 2. Nanocrystalline Cellulose (NCC-FP) Nanocrystalline Cellulose from Canadian wood sources As received: low density translucent flakes water soluble at a few wt% 200nm x 10nm fibers2
4
J. RETTENMAIER & SÖHNE GMBH+CO.KG 3. UltraFine Cellulose 100 (UFC-100)
Microcrystalline cellulose As received: small off-white flakes (~1mm)
water dispersible at few wt%
~4.5um microfibers
4. NanoDisperse Cellulose (MF 40-10)
Nano/Microcrystalline Cellulose
As received: dispersion, white paste
~1-5um microfibers
Methods Thermogravimetric Analysis (TGA)
Weight change of cellulose as a function of a preprogrammed heating profile Thermal degradation is proportional to the conversion of cellulose from solid to gaseous products Temperature: 35-600ºC Heating rates: 5, 10, 20, 30, 40ºC per minute Gas atmosphere: Air and N2
5
Methods Flynn-Wall-Ozawa3
6
Determine activation energy as a kinetic parameter of thermal degradation EA determined from plot of log β versus -1/RT at a constant conversion (over multiple heating rates) and will result in a line with a slope of 0.4567*EA Focus on initial section of conversion (0.98 EA lines nearly parallel and constant, confirming that the activation energies do not depend on previous conversion (except NCC-Alb)
NCC-FP > MF 40-10 > UFC-100 > NCC-Alb varied from 204.7 to 111.9 kJ/mol between the NCC-FP and NCC-Alb inconsistency and lower magnitude for the NCC-Alb source can be associated to inclusions of lignin, hemi-cellulose, or some other impurity
Results: Moisture Content
Each cellulose source was tested for moisture content on four random days
17
The standard deviations are low as the %MC did not fluctuate too dramatically during the testing.
Conclusions
EA for EA for EA for EA for
NCC-Alb were 122 kJ/mol and 130 kJ/mol in air and nitrogen respectively NCC-FP were were higher at 184 and 202 kJ/mol for air and nitrogen UFC-100 were were higher at 136 and 145 kJ/mol for air and nitrogen MF 40-10 were were higher at 152 and 166 kJ/mol for air and nitrogen
NCC-FP and UFC-100 sample contained less impurities than the other sources
UFC-100 had the highest Onset of Degradation followed by NCC-FP, MF 40-10, and NCC-Alb
EA for NCC-Alb appeared more dependent on conversion than the other cellulose sources
18
EA and Onset of Degradation temperature was calculated for NCC-Alb, NCC-FP, UFC100 and MF 40-10 using Flynn-Wall-Ozawa method
The calculated EA and onset temperatures can be used to model and predict mass loss during a specific processing temperature profile as well as screening for the best candidate to use in a polymer nanocomposite5 The moisture content for NCC-Alb is approximately 4.9%; for NCC-FP it is slightly higher at 6.4%; and UFC-100 and MF 40-10 had %MC of 6.3% and 5.7% respectively
Acknowledgements The authors would also like to thank FP Innovations, Alberta Innovates, and JRS Inc. for donating the cellulose samples; and acknowledge financial support from the Natural Science and Engineering Council of Canada (Discovery Grant) and the Ontario Ministry of Research and Innovation (The Ontario BioCar Initiative).
References M.A. Hubbe, O.J. Rojas, L.A. Lucia, and M. Sain, “Cellulosic nanocomposites: A Review,” BioResources, vol. 3, 2008, pp. 929-980. FP Innovations. 2008. Nanocrystalline Cellulose – ‘Green’ Nanoparticles. Brochure. Pointe-Claire, PQ. JRS Inc., “UFC-100 Material Specification Sheet,” 2010. JRS Inc., “MF 40-10 Material Specification Sheet,” 2010. T. Ozawa, “Kinetic analysis of derivative curves in thermal analysis,” Journal of Thermal Analysis, vol. 2, Sep. 1970, pp. 301-324. M. Golbabaie, “Characterization of Ontario Crop Fibres for Use in Biocomposites (Wheat and Soybean),” University of Guelph. MSc Thesis. 2008. 7. D.K. Misra. In: F. Hamilton, B. Leopold and M.J. Kocurek, Editors, (Version 5 Edition ed.),Pulp and Paper Manufacture Vol. 3, Joint Textbook Committee of the Paper Industry TAPPI-CPPA, Montreal, Canada (1987), pp. 82–93 Secondary Fibers and Nonwood Pulping .
1. 2. 3. 4. 5. 6.
19
Thank you PRESENTED BY
Andrew C. Finkle MASc ChemEng (Nano)
University of Waterloo [email protected]
Please remember to turn in your evaluation sheet...
