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A Study of Aged Carbon Nanotubes by Thermogravimetric Analysis
                                                                        E. Sahle-Demessie, A. Zhao, U.S. EPA, Office of Research and Development National Risk Management Research Laboratory Cincinnati, OH 45268
                                                                        Andrew W. Salamon, PerkinElmer Corp. , Shelton, CT

                                                                                             Table 1 MWNT Characterization
    1                                                                                                                                              Three “ A” samples in figure 5 were exposed to UV for:                        7     Summary
        Carbon Nanotubes                                                  TYPE      Purity       Outside        Length     Specific Surface        • An exposure of 9.0 hours
                                                                                                                                                                                                                             Based on the Pyris 1 TGA data collected, UV light has an effect on
 Increased use of carbon nanotubes (CNTs) in consumer and                                        Diameter                       Area               • An exposure of 5.5 hours
                                                                                                                                                                                                                             CNTs. As this study suggests, the longer the CNTs are subjected to UV
 industrial products have scientists asking about the implications of    Type A     >95%          8-15 nm       ~50µm         >233 m2/g            • An exposure of 4.0 hours
 CNTs in our environment. End product applications include                                                                                                                                                                   light, the sooner CNTs decompose when heated to elevated
                                                                         Type B     >95%         10-20 nm      10-30 µm       >200 m2/g                                                                                      temperatures.
 Polymer Composites, Drug Delivery Systems, Coatings and Films,
 Electronic components, Cosmetics, amongst others.
                                                                         Type C     >95%          > 50 nm      10-20 µm       >40 m2/g              6     Results
                                                                        Table 1 is the manufacturer’s product description before the samples       This experiment results in the CNT amorphous carbon decomposing
                                                                                                                                                                                                                                 8     Conclusion
 Thermogravimetry a simple analytical technique that is frequently
 used to characterize carbon nanotubes.[1] The Pyris 1 TGA              were subjected to UV aging. The far right column explains one of the       before the structural carbon. All carbon should decompose in the          Thermogravimetry by the Pyris 1 TGA is a simple analytical technique.
 delivers quick and accurate results.                                   foremost features of NMs, that is their high surface area in               oxidative environment before reaching 900°C.                              Its low mass furnace delivers quick and accurate results for carbon
                                                                        relationship to it weight. One gram of Type B CNTs have a surface                                                                                    nanotube analysis.
                                                                        area that is larger than 200 square meters (>200m2/g). The
    2    Carbon Nanotube Life Cycle                                     manufacturer’s CNT outside diameters are verified by the TEM
 During the CNT life cycle: synthesis, end-product formulation, end-    image in Figure 2.
 use, and product end-of-life, CNTs may enter the environment.
                                                                           4   Characterization of nanotubes by TGA
                                                                        Thermogravimetric Analysis was the first analytical technique chosen
                                                                        to compare the effects of the UV exposure times on the CNTs. TGA
                                                                        is very simple, yet a very accurate analytical technique that delivers
                                                                        results quickly. Studying the oxidation of fullerene C60 using TGA has
                                                                        been reported [4-6]. The high sensitivity of the TGA, which is in the
                                                                        order of 0.1 microgram/min, permitted weight loss determinations at
                                                                        a given heating rate, within a short time without consuming too much
                                                                        material. The oxidation rates of carbon nanotubes measured in air at
                                                                        atmospheric pressure within the TGA are unique for each CNT
                                                                        sample of different wall thicknesses. Figure 5 shows the
                                                                        decomposition temperatures (i.e. oxidation) for samples run at the
                                                                        same heating rate, varies up to ±40 oC depending on the                    Figure 4: X Axis = Temperature: When observing Thermogravimetric
                                                                        characteristics of the carbon tubes.                                       weight loss curves in regards to temperature, the weight loss curves
                                                                                                                                                   above indicate that CNTs exposed to UV light for 9 hours began
                                                                                                                                                   decomposition at a lower temperature than the other two samples of
                                                                                                                                                   shorter exposures.
Figure 1: This carbon nanotube life cycle diagram depicts waste
entering the environment during production through product end-use.

    3    Materials Used
Commercially available high purity MWCNT samples were obtained.
Analysis of acid washed samples using ICP showed less than 1% of
trace elements.                                                                                                                                                                                                                                                                               Pyris 1 TGA




                                                                                                                                                                                                                             Acknowledgement:
                                                                                                                                                                                                                             Special thanks to E. Sahle-Demessie and A. Zhao of the US EPA, January 2011,
                                                                         Figure 3 Thermogravimetric analysis of CNTs showing weight loss                                                                                     for providing the Pyris 1 TGA data. This thermogravimetric data is from an on-
                                                                         curves. Sample weight was about 10 mg, oxygen flow was 20                                                                                           going study of environmental effects on carbon nanotubes.
                                                                         mL/min. Samples A, B, C, had varying wall thicknesses
                                                                                                                                                                                                                             References:
                                                                                                                                                                                                                             1. Mansfield, E., Kar, A., Hooker, S. A., Applications of TGA in Quality control of SWCNTs, Analytical
                                                                           5      Measuring Aging of Carbon Nanotubes                              Figure 5: X Axis = Time: To gain a better understanding of the results,      and Bioanalytical Chemistry, Vol 369, Number 3, 1071-1077, 2009.
                                                                                                                                                   the same data file is displayed on a Time X-axis. The 1st derivative      2. Ozin, G. A., Arsenault, A. C., and Cademartiri, L., Nanochemistry – A Chemical Approach to
                                                                                                                                                                                                                                Nanomaterials, Royal Society of Chemistry, Cambridge, UK, 2009. Page 209.
                                                                         In a laboratory environment, three high purity MWCNT samples that         curve of each weight loss curve is displayed. The 1st derivative is a     3. National Nanotechnology Initiative – Human Health Workshop, November 2009, Washington,
                                                                         had no specific wrap were analyzed. They were all nearly the same         widely used tool to compliment TGA weight loss curve, and like the           D.C., USA.
                                                                                                                                                                                                                             4. Pang L. S. K., Saxby, J. D., and Chatfield, S. P., Thermogravimetric Analysis of Carbon
Figure 2: Above, the Transmission Electron Microscope (TEM)              weight and came from the same manufacturing lot. They were                weight loss curve, the 1st derivative curve is very reproducible. Upon       Nanotubes and Nanoparticles, J. Physical Chemistry, 97, 27, 1993.
image of CNTs indicates that the CNTs have a ~ 20nm outside              subjected to the same UV light source. The intent of the UV light is to   examination of the 1st derivative curves above, the CNT sample with       5. Saxby, J. D., Chatfield, S. P., and et al, Thermogravimetric analysis of Buckminsterfullernce and
                                                                                                                                                   the longest UV exposure decomposes more than 5 minutes before the            Related Materials in Air, J. Phys. Chem. 1992, 96,17-18.
diameter and their lengths are much larger than 200nm.                   simulate sunlight in a controlled manner.                                                                                                           6. Joshi, A., Nimmagadda, R., and Herrington, J., Oxidation Kinetics of Diamond, Graphite and
                                                                                                                                                   other two samples of shorter exposures.                                      Chemical Vapor Deposited Diamond Films by Thermal Gravimetry, J. Vac. Sci. Technol. A 8(3),
                                                                                                                                                                                                                                May/June, 1990.


                                                                                                                                                                             PerkinElmer, Inc., 940 Winter Street, Waltham, MA USA (800) 762-4000 or (+1) 203 925-4602 www.perkinelmer.com

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PerkinElmer: A Study of Aged Carbon Nanotubes by Thermogravimetric Analysis

  • 1. A Study of Aged Carbon Nanotubes by Thermogravimetric Analysis E. Sahle-Demessie, A. Zhao, U.S. EPA, Office of Research and Development National Risk Management Research Laboratory Cincinnati, OH 45268 Andrew W. Salamon, PerkinElmer Corp. , Shelton, CT Table 1 MWNT Characterization 1 Three “ A” samples in figure 5 were exposed to UV for: 7 Summary Carbon Nanotubes TYPE Purity Outside Length Specific Surface • An exposure of 9.0 hours Based on the Pyris 1 TGA data collected, UV light has an effect on Increased use of carbon nanotubes (CNTs) in consumer and Diameter Area • An exposure of 5.5 hours CNTs. As this study suggests, the longer the CNTs are subjected to UV industrial products have scientists asking about the implications of Type A >95% 8-15 nm ~50µm >233 m2/g • An exposure of 4.0 hours CNTs in our environment. End product applications include light, the sooner CNTs decompose when heated to elevated Type B >95% 10-20 nm 10-30 µm >200 m2/g temperatures. Polymer Composites, Drug Delivery Systems, Coatings and Films, Electronic components, Cosmetics, amongst others. Type C >95% > 50 nm 10-20 µm >40 m2/g 6 Results Table 1 is the manufacturer’s product description before the samples This experiment results in the CNT amorphous carbon decomposing 8 Conclusion Thermogravimetry a simple analytical technique that is frequently used to characterize carbon nanotubes.[1] The Pyris 1 TGA were subjected to UV aging. The far right column explains one of the before the structural carbon. All carbon should decompose in the Thermogravimetry by the Pyris 1 TGA is a simple analytical technique. delivers quick and accurate results. foremost features of NMs, that is their high surface area in oxidative environment before reaching 900°C. Its low mass furnace delivers quick and accurate results for carbon relationship to it weight. One gram of Type B CNTs have a surface nanotube analysis. area that is larger than 200 square meters (>200m2/g). The 2 Carbon Nanotube Life Cycle manufacturer’s CNT outside diameters are verified by the TEM During the CNT life cycle: synthesis, end-product formulation, end- image in Figure 2. use, and product end-of-life, CNTs may enter the environment. 4 Characterization of nanotubes by TGA Thermogravimetric Analysis was the first analytical technique chosen to compare the effects of the UV exposure times on the CNTs. TGA is very simple, yet a very accurate analytical technique that delivers results quickly. Studying the oxidation of fullerene C60 using TGA has been reported [4-6]. The high sensitivity of the TGA, which is in the order of 0.1 microgram/min, permitted weight loss determinations at a given heating rate, within a short time without consuming too much material. The oxidation rates of carbon nanotubes measured in air at atmospheric pressure within the TGA are unique for each CNT sample of different wall thicknesses. Figure 5 shows the decomposition temperatures (i.e. oxidation) for samples run at the same heating rate, varies up to ±40 oC depending on the Figure 4: X Axis = Temperature: When observing Thermogravimetric characteristics of the carbon tubes. weight loss curves in regards to temperature, the weight loss curves above indicate that CNTs exposed to UV light for 9 hours began decomposition at a lower temperature than the other two samples of shorter exposures. Figure 1: This carbon nanotube life cycle diagram depicts waste entering the environment during production through product end-use. 3 Materials Used Commercially available high purity MWCNT samples were obtained. Analysis of acid washed samples using ICP showed less than 1% of trace elements. Pyris 1 TGA Acknowledgement: Special thanks to E. Sahle-Demessie and A. Zhao of the US EPA, January 2011, Figure 3 Thermogravimetric analysis of CNTs showing weight loss for providing the Pyris 1 TGA data. This thermogravimetric data is from an on- curves. Sample weight was about 10 mg, oxygen flow was 20 going study of environmental effects on carbon nanotubes. mL/min. Samples A, B, C, had varying wall thicknesses References: 1. Mansfield, E., Kar, A., Hooker, S. A., Applications of TGA in Quality control of SWCNTs, Analytical 5 Measuring Aging of Carbon Nanotubes Figure 5: X Axis = Time: To gain a better understanding of the results, and Bioanalytical Chemistry, Vol 369, Number 3, 1071-1077, 2009. the same data file is displayed on a Time X-axis. The 1st derivative 2. Ozin, G. A., Arsenault, A. C., and Cademartiri, L., Nanochemistry – A Chemical Approach to Nanomaterials, Royal Society of Chemistry, Cambridge, UK, 2009. Page 209. In a laboratory environment, three high purity MWCNT samples that curve of each weight loss curve is displayed. The 1st derivative is a 3. National Nanotechnology Initiative – Human Health Workshop, November 2009, Washington, had no specific wrap were analyzed. They were all nearly the same widely used tool to compliment TGA weight loss curve, and like the D.C., USA. 4. Pang L. S. K., Saxby, J. D., and Chatfield, S. P., Thermogravimetric Analysis of Carbon Figure 2: Above, the Transmission Electron Microscope (TEM) weight and came from the same manufacturing lot. They were weight loss curve, the 1st derivative curve is very reproducible. Upon Nanotubes and Nanoparticles, J. Physical Chemistry, 97, 27, 1993. image of CNTs indicates that the CNTs have a ~ 20nm outside subjected to the same UV light source. The intent of the UV light is to examination of the 1st derivative curves above, the CNT sample with 5. Saxby, J. D., Chatfield, S. P., and et al, Thermogravimetric analysis of Buckminsterfullernce and the longest UV exposure decomposes more than 5 minutes before the Related Materials in Air, J. Phys. Chem. 1992, 96,17-18. diameter and their lengths are much larger than 200nm. simulate sunlight in a controlled manner. 6. Joshi, A., Nimmagadda, R., and Herrington, J., Oxidation Kinetics of Diamond, Graphite and other two samples of shorter exposures. Chemical Vapor Deposited Diamond Films by Thermal Gravimetry, J. Vac. Sci. Technol. A 8(3), May/June, 1990. PerkinElmer, Inc., 940 Winter Street, Waltham, MA USA (800) 762-4000 or (+1) 203 925-4602 www.perkinelmer.com