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Homogeneous nanocellular foams from styrenic-acrylic polymer blends

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Abstract

Nano-cellular foams were successfully produced from blends of styrenic and acrylic polymers by a two-step batch foaming process using carbon dioxide as the blowing agent. Addition of poly(ethyl methacrylate) or poly(methyl methacrylate-co-ethyl acrylate) to styrene-acrylonitrile copolymers, even at a low level, resulted in very homogeneous foams with smaller cell size and narrower cell size distribution than with the individual polymers. The best nanofoams produced from miscible blends have average cell sizes below 100 nm, cell densities up to 5 × 1015 cm−3 and medium-to-low relative densities (void fraction between 60 and 70%). Contrary to previous studies, it was found that blends with lower CO2 solubility gave higher cell density nanofoams. This suggests new mechanisms for the nucleation of foams from these blends at the nanoscale.

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References

  1. A.S. Zalusky, R. Olayo-Valles, C.J. Taylor, and M.A. Hillmyer: Mesoporous polystyrene monoliths. J. Am. Chem. Soc. 123(7), 1519 (2001).

    Article  CAS  Google Scholar 

  2. A.S. Zalusky, R. Olayo-Valles, J.H. Wolf, and M.A. Hillmyer: Ordered nanoporous polymers from polystyrene−polylactide block copolymers. J. Am. Chem. Soc. 124(43), 12761 (2002).

    Article  CAS  Google Scholar 

  3. H. Yokoyama and K. Sugiyama: Nanocellular structures in block copolymers with CO2-philic blocks using CO2 as a blowing agent: Crossover from micro- to nanocellular structures with depressurization temperature. Macromolecules 38(25), 10516 (2005).

    Article  CAS  Google Scholar 

  4. B. Krause, R. Mettinkhof, N.F.A. van der Vegt, and M. Wessling: Microcellular foaming of amorphous high-Tg polymers using carbon dioxide. Macromolecules 34(4), 874 (2001).

    Article  CAS  Google Scholar 

  5. D. Miller, P. Chatchaisucha, and V. Kumar: Microcellular and nanocellular solid-state polyetherimide (PEI) foams using sub-critical carbon dioxide I. Processing and structure. Polymer 50(23), 5576 (2009).

    Article  CAS  Google Scholar 

  6. D. Miller and V. Kumar: Microcellular and nanocellular solid-state polyetherimide (PEI) foams using sub-critical carbon dioxide II. Tensile and impact properties. Polymer 52(13), 2910 (2011).

    Article  CAS  Google Scholar 

  7. L.W. Hrubesh and R.W. Pekala: Thermal properties of organic and inorganic aerogels. J. Mater. Res. 9(3), 731 (1994).

    Article  CAS  Google Scholar 

  8. T. Otsuka, K. Taki, and M. Ohshima: Nanocellular foams of PS/PMMA polymer blends. Macromol. Mater. Eng. 293(1), 78 (2008).

    Article  CAS  Google Scholar 

  9. H. Ruckdäschel, P. Gutmann, V. Altstädt, H. Schmalz, and A. Müller: Foaming of microstructured and nanostructured polymer blends. Adv. Polym. Sci. 227, 199 (2010).

    Article  Google Scholar 

  10. J.A. Reglero Ruiz, M. Dumon, J. Pinto, and M.A. Rodriguez-Pérez: Low-density nanocellular foams produced by high-pressure carbon dioxide. Macromol. Mater. Eng. 296(8), 752 (2011).

    Article  CAS  Google Scholar 

  11. J.A. Reglero Ruiz, M. Pedros, J-M. Tallon, and M. Dumon: Micro and nano cellular amorphous polymers (PMMA, PS) in supercritical CO2 assisted by nanostructured CO2-philic block copolymers - one step foaming process. J. Supercrit. Fluids 58(1), 168 (2011).

    Article  Google Scholar 

  12. J. Pinto, M.A. Rodríguez-Pérez, J.A. de Saja, M. Dumon, R. García, and C. Dietz: Relationship between the nano-structured morphology of PMMA/MAM blends and the nanocellular structure of foams produced from these materials. Presented at The Society of Plastics Engineers FOAMS 2011 Conference, Iselin, NJ, September 2011.

  13. S. Costeux: Nanoporous polymeric foam having high porosity. Int. Patent Appl. WO 2011066060, filed November 25, 2009 (33 pp.), assigned to Dow Global Technologies LLC, USA.

  14. S. Costeux and L. Zhu: Thermoplastic nanocellular foams with low relative density using CO2 as the blowing agent. Presented at The Society of Plastics Engineers FOAMS 2011 Conference, Iselin, NJ, September 2011.

  15. S. Costeux and L. Zhu: Low density thermoplastic nanofoams nucleated by nanoparticles. Polymer 54(11), 2785 (2013).

    Article  CAS  Google Scholar 

  16. S. Costeux: Nanoporous Polymeric foam having high cell density without nanofiller. Int. Patent Appl. WO 2011112352, filed March 10, 2010 (32 pp.), assigned to Dow Global Technologies LLC, USA.

  17. S. Costeux, H. Jeon, S. Bunker, and I. Khan: Nanocellular foams from acrylic polymers: Experiments and modeling. Presented at The Society of Plastics Engineers FOAMS 2012 Conference, Barcelona, Spain, September 2012.

  18. M.E. Fowler, J.W. Barlow, and D.R. Paul: Effect of copolymer composition on the miscibility of blends of styrene-acrylonitrile copolymers with poly (methyl methacrylate). Polymer 28(7), 1177 (1987).

    Article  CAS  Google Scholar 

  19. M. Suess, J. Kressler, and H.W. Kammer: The miscibility window of poly(methylmethacrylate)/poly(styrene-co-acrylonitrile) blends. Polymer 28(6), 957 (1987).

    Article  CAS  Google Scholar 

  20. S. Costeux: Polymeric nanofoam containing acrylonitrile-based copolymers blends with (meth)acrylic polymers. Int. Patent Appl. WO 2013048761, filed September 30, 2011 (20 pp.), assigned to Dow Global Technologies LLC, USA.

  21. H.E. Park and J.M. Dealy: Effects of pressure and supercritical fluids on the viscosity of polyethylene. Macromolecules 39(16), 5438 (2006).

    Article  CAS  Google Scholar 

  22. V. Kumar and N.P. Suh: A process for making microcellular thermoplastic parts. Polym. Eng. Sci. 30(20), 1323 (1990).

    Article  CAS  Google Scholar 

  23. J.S. Colton and N.P. Suh: The nucleation of microcellular thermoplastic foam with additives. Part I. Theoretical considerations. Polym. Eng. Sci. 27(7), 485 (1987).

    Article  CAS  Google Scholar 

  24. C. Dutriez, K. Satoh, M. Kamigaito, and H. Yokoyama: Nanocellular foaming of fluorine containing block copolymers in carbon dioxide: The role of glass transition in carbon dioxide. RSC Adv. 2, 2821 (2012).

    Article  CAS  Google Scholar 

  25. P.D. Condo and K.P. Johnston: Retrograde vitrification of polymers with compressed fluid diluents: Experimental confirmation. Macromolecules 25(24), 6730 (1992).

    Article  CAS  Google Scholar 

  26. T.A. Walker, Y.B. Melnichenko, G.D. Wignall, J.S. Lin, and R.J. Spontak: Phase behavior of poly(methyl methacrylate)/poly(vinylidene fluoride) blends in the presence of high-pressure carbon dioxide. Macromol. Chem. Phys. 204(17), 2064 (2003).

    Article  CAS  Google Scholar 

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Acknowledgments

This material is based on the work supported by the U.S. Department of Energy under Grant No. DE-EE0003916. The Dow chemical Company is acknowledged for permission to publish this work. We thank the following Dow colleagues for analytical support: Diego Cristancho for MSB data, Cliff Todd for high resolution SEM imaging, Philip Lin for STXM measurements, and Anand Badami for TEM imaging. High pressure viscosity measurements were carried out by Dr. Hee-Eon Park at McGill University, Montreal (Canada). We are grateful to Prof. Zhen-Gang Wang (California Institute of Technology) and Prof. Nitash Balsara (University of California Berkeley) for many stimulating discussions on the complex behavior of polymer/CO2 systems.

Disclaimer: This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

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Authors and Affiliations

  1. Dow Coatings & Construction, The Dow Chemical Company, Midland, Michigan, 48674, USA

    Stéphane Costeux & Shana P. Bunker

  2. The Dow Chemical Company, Dow Electronic Materials, Dow Seoul Technology Center, Hwaseong-si, Gyeonggi-do, 445-170, Korea

    Hyun K. Jeon

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  1. Stéphane Costeux
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Correspondence to Stéphane Costeux.

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Costeux, S., Bunker, S.P. & Jeon, H.K. Homogeneous nanocellular foams from styrenic-acrylic polymer blends. Journal of Materials Research 28, 2351–2365 (2013). https://doi.org/10.1557/jmr.2013.100

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