A pilot interlaboratory comparison of protocols that simulate aging of nanocomposites and detect released fragments
Wendel Wohlleben A E , Gemma Vilar B , Elisabet Fernández-Rosas B , David González-Gálvez B , Claus Gabriel C , Sabine Hirth A , Thomas Frechen A , Deborah Stanley D , Justin Gorham D , Li-Piin Sung D , Hsiang-Chun Hsueh D , Yu-Fan Chuang D , Tinh Nguyen D E and Socorro Vazquez-Campos B E
+ Author Affiliations
- Author Affiliations
A BASF SE, Advanced Materials and Systems Research, Department of Material Physics, D-67056 Ludwigshafen, Germany.
B LEITAT Technological Center, c/de la Innovació 2, E-08225 Terrassa (Barcelona), Spain.
C BASF SE, Advanced Materials and Systems Research, Department of Structural Materials, D-67056 Ludwigshafen, Germany.
D National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA.
E Corresponding authors. Email: wendel.wohlleben@basf.com; tinh.nguyen@nist.gov; svazquez@leitat.org
Environmental Chemistry 11(4) 402-418 https://doi.org/10.1071/EN14072
Submitted: 5 April 2014 Accepted: 28 June 2014 Published: 8 August 2014
Environmental context. Nanoparticles are contained in many commercialised products, but the lack of validated methods to assess their potential release into the environment hampers our ability to perform a reliable risk assessment. Equipment to simulate aging is available, but the challenge is to sample released entities, and to analyse those fragments with suitable nano-analytics. We describe methods to characterise the degradation and surface accumulation of nanoparticles, and to quantify fragments released during UV irradiation of polymer nanocomposites.
Abstract. The safe use of nanoparticles as fillers in nanocomposite materials depends, in part, on a good understanding of what is released from aging nanocomposites, and at which rate. Here we investigated the critical parameters of the nanoparticle release phenomenon by a pilot inter-laboratory study of a polyamide containing 4 mass % of silica nanoparticles (nanosilica). The main focus is on the validity range of the aging and release protocols. Both induced release by mechanical shear after dry weathering at different UV intensities and spontaneous release during wet weathering were investigated. We propose a combined protocol based on the finding that the characteristics of released fragments – which are the essential input for fate, transport and (eco-)toxicological testing – were reproducible between laboratories and between different aging, sampling and analysis protocols: the released fragments were a polydisperse mixture of predominantly composite fragments from the nanometre up to several micrometre diameter, and of clustered or individual nanosilica unbound to polymer. The unbound fraction was microscopically observed but could not be quantified. We found that aging conditions are very critical for the release rates, not for release characteristics. The sampling protocol tolerates some differences. Simplified aging + immersion protocols can at least partially replace, complement and extend dedicated weathering apparatus with run-off collection.
Additional keywords: dry aging, lifecycle, nanosilica, polyamide, release, wet aging.
References
[1] B. Nowack, B. Ranville, S. Diamond, J. A. Galego-Urrea, C. Metcalfe, J. Rose, N. Horne, A. A. Koelmans, S. J. Klaine, Potential scenarios for nanomaterial release and subsequent alteration in the environment. Environ. Toxicol. Chem. 2012, 31, 50.| Potential scenarios for nanomaterial release and subsequent alteration in the environment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhs1yktr7M&md5=b3977061ab625444afef30ec0a3da937CAS | 22038832PubMed |
[2] M. R. Wiesner, G. V. Lowry, K. L. Jones, M. F. Hochella, R. T. di Giulio, E. Casman, E. S. Bernhardt, Decreasing uncertainties in assessing environmental exposure, risk, and ecological implications of nanomaterials. Environ. Sci. Technol. 2009, 43, 6458.
| Decreasing uncertainties in assessing environmental exposure, risk, and ecological implications of nanomaterials.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXptFCiur0%3D&md5=0886f221938034ce9537d754f6700ef7CAS | 19764202PubMed |
[3] E. J. Petersen, L. Zhang, N. Mattison, D. O’Carroll, A. Whelton, N. Uddin, T. Nguyen, Q. Huang, T. Henry, R. Holbrook, K. Chen, Potential release pathways, environmental fate, and ecological risks of carbon nanotubes. Environ. Sci. Technol. 2011, 45, 9837.
| Potential release pathways, environmental fate, and ecological risks of carbon nanotubes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtlyhurrK&md5=cadee60329871a9e167a4d0a0fd59924CAS | 21988187PubMed |
[4] T. Nguyen, W. Wohlleben, L. Sung, Mechanisms of aging and release from weathered nanocomposites, in Safety of Nanomaterial along their Lifecycle: Release, Exposure and Human Hazards (Eds W. Wohlleben, T. Kuhlbusch, C. M. Lehr, J. Schnekenburger) 2014, Ch. 14, pp. 315–334 (Taylor & Francis: boca Raton, FL).
[5] T. Nguyen, B. Pellegrin, C. Bernard, X. Gu, J. M. Gorham, P. Stutzman, D. Stanley, A. Shapiro, E. Byrd, R. Hettenhouser, J. Chin, Fate of nanoparticles during life cycle of polymer nanocomposites. J. Phys. Conf. Ser. 2011, 304, 012060.
| Fate of nanoparticles during life cycle of polymer nanocomposites.Crossref | GoogleScholarGoogle Scholar |
[6] J. P. Kaiser, M. Roesslein, L. Diener, P. Wick, Human health risk of ingested nanoparticles that are added as multifunctional agents to paints: an in vitro study. PLoS ONE 2013, 8, e83215.
| Human health risk of ingested nanoparticles that are added as multifunctional agents to paints: an in vitro study.Crossref | GoogleScholarGoogle Scholar | 24358264PubMed |
[7] A. Al-Kattan, A. Wichser, R. Vonbank, S. Brunner, A. Ulrich, S. Zuin, Y. Arroyo, L. Golanski, B. Nowack, Characterization of materials released into water from paint containing nano-SiO2. Chemosphere
| Characterization of materials released into water from paint containing nano-SiO2.Crossref | GoogleScholarGoogle Scholar |
[8] B. Nowack, R. M. David, H. Fissan, H. Morris, J. A. Shatkin, M. Stintz, R. Zepp, D. Brouwer, Potential release scenarios for carbon nanotubes used in composites. Environ. Int. 2013, 59, 1.
| Potential release scenarios for carbon nanotubes used in composites.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhtl2qtbfI&md5=01d910ccc058c3302165c1cce0a8cd31CAS | 23708563PubMed |
[9] E. J. Petersen, T. Lam, J. M. Gorham, K. C. Scott, C. J. Long, D. Stanley, R. Sharma, J. Alexander Liddle, B. Pellegrin, T. Nguyen, Methods to assess the impact of UV irradiation on the surface chemistry and structure of multiwall carbon nanotube epoxy nanocomposites. Carbon 2014, 69, 194.
| Methods to assess the impact of UV irradiation on the surface chemistry and structure of multiwall carbon nanotube epoxy nanocomposites.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXitVWhsLrJ&md5=5ef6fca9da7168a373cf73a658ffb373CAS |
[10] W. Wohlleben, S. Brill, M. W. Meier, M. Mertler, G. Cox, S. Hirth, B. von Vacano, V. Strauss, S. Treumann, K. Wiench, L. Ma-Hock, R. Landsiedel, On the lifecycle of nanocomposites: comparing released fragments and their vivo hazard from three release mechanisms and four nanocomposites. Small 2011, 7, 2384.
| On the lifecycle of nanocomposites: comparing released fragments and their vivo hazard from three release mechanisms and four nanocomposites.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtVaisLfP&md5=b95fee68e582f253e082a507e3b8a1fdCAS | 21671434PubMed |
[11] W. Wohlleben, M. W. Meier, S. Vogel, R. Landsiedel, G. Cox, S. Hirth, Z. Tomovic, Elastic CNT-polyurethane nanocomposite: synthesis, performance and assessment of fragments released during use. Nanoscale 2013, 5, 369.[Published online 21 November 2012]
| Elastic CNT-polyurethane nanocomposite: synthesis, performance and assessment of fragments released during use.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhvVSktbrK&md5=632f6d0142fb272acc035dda54434b28CAS | 23172121PubMed |
[12] C. Kingston, R. Zepp, A. Andrady, D. Boverhof, R. Fehir, D. Hawkins, J. Roberts, P. Sayre, B. Shelton, Y. Sultan, V. Vejins, W. Wohlleben, Release characteristics of selected carbon nanotube polymer composites. Carbon 2014, 68, 33.[Published online early 26 November 2013]
| Release characteristics of selected carbon nanotube polymer composites.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhvFGitrvN&md5=d4406fd0bbecb4fb2d7c6f16d7453abaCAS |
[13] C. Bernard, T. Nguyen, B. Pellegrin, R. D. Holbrook, M. Zhao, J. Chin, Fate of graphene in polymer nanocomposite exposed to UV radiation. J. Phys. Conf. Ser. 2011, 304, 012063.
| Fate of graphene in polymer nanocomposite exposed to UV radiation.Crossref | GoogleScholarGoogle Scholar |
[14] J. Lemaire, J. L. Gardette, A. Rivaton, A. Roger, Dual photo-chemistries in aliphatic polyamides, bisphenol A polycarbonate and aromatic polyurethanes – a short review. Polym. Degrad. Stabil. 1986, 15, 1.
| Dual photo-chemistries in aliphatic polyamides, bisphenol A polycarbonate and aromatic polyurethanes – a short review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL28XkvFOqtLk%3D&md5=97fbfa4df2d775eb1a23d5ce33e2d1a7CAS |
[15] J. F. Rabek, Polymer Photodegradation: Mechanisms And Experimental Methods 1995, pp. 296–306 (Springer: New York).
[16] A. Roger, D. Sallet, J. Lemaire, Photochemistry of aliphatic polyamides. 4. Mechanisms of photooxidation of polyamides 6, 11, and 12 at long wavelengths. Macromol. 1986, 19, 579.
| Photochemistry of aliphatic polyamides. 4. Mechanisms of photooxidation of polyamides 6, 11, and 12 at long wavelengths.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL28XhtFSgsro%3D&md5=ec01069046bfede069a09a7c3f65f619CAS |
[17] M. Busquets-Fité, E. Fernandez, G. Janer, G. Vilar, S. Vazquez-Campos, R. Zanasca, C. Citterio, L. Mercante, V. Puntes, Exploring release and recovery of nanomaterials from commercial polymeric nanocomposites. J. Phys. Conf. Ser. 2013, 429, 012048.
| Exploring release and recovery of nanomaterials from commercial polymeric nanocomposites.Crossref | GoogleScholarGoogle Scholar |
[18] S. Hirth, L. G. Cena, G. Cox, Z. Tomovic, T. M. Peters, W. Wohlleben, Scenarios and methods that induce protruding or released CNTs after degradation of composite materials. J. Nanopart. Res. 2013, 15, 1504.
| Scenarios and methods that induce protruding or released CNTs after degradation of composite materials.Crossref | GoogleScholarGoogle Scholar | 23596358PubMed |
[19] L. Scifo, P. Chaurand, A. Masion, M. Auffan, M.-A. Diot, J. Labille, J. Y. Bottero, J. Rose, Release of CeO2 nanoparticles upon aging of acrylic wood coatings. Presented at NanoSafe2012, 15 November 2012, Grenoble, 2012. Available at http://www.nanosafe.org/scripts/home/publigen/content/templates/show.asp?P=143&L=EN&ITEMID=57 [Verified 15 July 2014].
[20] T. Nguyen, Quantitative studies of photo-induced surface accumulation and release of nanoparticles in polymer nanocomposites. Presented at NanoSafe2012, 15 November 2012, Grenoble, 2012. Available at http://www.nanosafe.org/scripts/home/publigen/content/templates/show.asp?P=143&L=EN&ITEMID=57 [Verified 15 July 2014].
[21] D. Göhler, A. Nogowski, P. Fiala, M. Stintz, Nanoparticle release from nanocomposites due to mechanical treatment at two stages of the life-cycle. J. Phys. Conf. Ser. 2013, 429, 012045.
| Nanoparticle release from nanocomposites due to mechanical treatment at two stages of the life-cycle.Crossref | GoogleScholarGoogle Scholar |
[22] ISO 4892–2: Plastics — Methods of Exposure to Laboratory Light Sources. Part 2: Xenon-Arc Lamps 2006. [Updated 2013].
[23] J. Chin, E. Byrd, N. Embree, J. Garver, B. Dickens, T. Finn, J. Martin, Accelerated UV weathering device based on integrating sphere technology. Rev. Sci. Instrum. 2004, 75, 4951.
| Accelerated UV weathering device based on integrating sphere technology.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXpslCls7k%3D&md5=cc465ddc33bc2cf153a49c9d9cae5a0eCAS |
[24] W. Wohlleben, Validity range of centrifuges for the regulation of nanomaterials: from classification to as-tested coronas. J. Nanopart. Res. 2012, 14, 1300.
| Validity range of centrifuges for the regulation of nanomaterials: from classification to as-tested coronas.Crossref | GoogleScholarGoogle Scholar | 23239934PubMed |
[25] R. P. Carney, J. Y. Kim, H. Qian, R. Jin, H. Mehenni, F. Stellacci, O. M. Bakr, Determination of nanoparticle size distribution together with density or molecular weight by 2D analytical ultracentrifugation. Nature Commun. 2011, 2, 335.
| Determination of nanoparticle size distribution together with density or molecular weight by 2D analytical ultracentrifugation.Crossref | GoogleScholarGoogle Scholar |
[26] P. N. Thanki, R. P. Singh, Progress in the area of degradation and stabilization of nylon 66. J. Macromol. Sci: Polym. Rev. 1998, 38, 595.
| Progress in the area of degradation and stabilization of nylon 66.Crossref | GoogleScholarGoogle Scholar |
[27] D. J. Skrovanek, S. E. Howe, P. C. Painter, M. M. Coleman, Hydrogen bonding in polymers: infrared temperature studies of an amorphous polyamide. Macromol. 1985, 18, 1676.
| Hydrogen bonding in polymers: infrared temperature studies of an amorphous polyamide.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2MXlt1CitL8%3D&md5=86f2eed8483d764181be2c89ce25670cCAS |
[28] N. B. Colthup, L. H. Daly, S. E. Wiberley, Introduction To Infrared And Raman Spectroscopy 1990 (Academic Press: San Diego, CA).
[29] T. Nguyen, B. Pellegrin, C. Bernard, P. Stutzman, J. M. Gorham, X. Gu, L. L. Yu, J. W. Chin, Characterization of surface accumulation and release of nanosilica during irradiation of polymer nanocomposites. J. Nanosci. Nanotechnol. 2012, 12, 6202.
| Characterization of surface accumulation and release of nanosilica during irradiation of polymer nanocomposites.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xht1OntbvJ&md5=e2b21b4a3c5795ee8c97e75a63503980CAS | 22962727PubMed |
[30] J. M. Gorham, T. Nguyen, C. Bernard, D. Stanley, R. D. Holbrook, Photo-induced surface transformations of silica nanocomposites. Surf. Interface Anal. 2012, 44, 1572.
| Photo-induced surface transformations of silica nanocomposites.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XovFWqs78%3D&md5=d8a4ffd6d1fa90c6811f3e83d7b418e5CAS |
[31] G. Vilar, E. Fernandez-Rosas, V. Puntes, V. Jamier, L. Aubouy, S. Vazquez-Campos, Monitoring migration and transformation of nanomaterials in polymeric composites during accelerated aging. J. Phys. Conf. Ser. 2013, 429, 012044.
| Monitoring migration and transformation of nanomaterials in polymeric composites during accelerated aging.Crossref | GoogleScholarGoogle Scholar |
[32] S. Froggett, S. Clancy, D. Boverhof, R. Canady, A review and perspective of existing research on the release of nanomaterials from solid nanocomposites. Part. Fibre Toxicol. 2014, 11, 17.
| A review and perspective of existing research on the release of nanomaterials from solid nanocomposites.Crossref | GoogleScholarGoogle Scholar | 24708765PubMed |
[33] S. Zuin, A. Massari, A. Ferrari, L. Golanski, Formulation effects on the release of silica dioxide nanoparticles from paint debris to water. Sci. Total Environ. 2014, 476–477, 298.
| Formulation effects on the release of silica dioxide nanoparticles from paint debris to water.Crossref | GoogleScholarGoogle Scholar | 24468504PubMed |
