A Marriage of Convenience: Uniting Polymer Chemistry and Polymer Physics to Craft Advanced, Functional Materials

A Marriage of Convenience: Uniting Polymer Chemistry and Polymer Physics to Craft Advanced, Functional Materials

Research Interests:

Research Aims

  i.                     Development and application of facile polymer synthesis methods

ii.                   Fundamental studies of self-assembly of functional nanoparticles and polymers

iii.                  Production and characterization of functional materials for energy and device applications

Motivation

Polymer nanocomposites (PNCs) have been successfully implemented in a variety of disparate areas such as aerospace, batteries, and biosensing. However, while there is a wide diversity of available polymers and nano-sized filler materials, PNCs are under-utilized, largely due to cost considerations. Developing PNCs into the commercial materials of the future necessitates the design, synthesis, and characterization of new, scalable combinations of polymers and nanosized fillers, which requires a fundamental understanding of the underlying physics that dictates matrix-filler interactions and the ability to modify the chemistry that can tune these interactions. Development and application of a versatile and facile polymer synthesis platform will allow for arbitrary control of polymer material properties and chemical functionality, which will allow us to tune matrix-filler interactions to control PNC properties and create novel, useful materials in a rational way.

Future Directions

As faculty, I want to unite polymer chemistry and polymer physics to create materials that solve real world problems. Specifically, I want to marry the polymer chemistry tools I have developed in my postdoctoral work with the soft matter physics training I received during my Ph.D. and apply this combination to rationally design, synthesize, characterize, and develop advanced materials with commercially relevant properties. My research goals are threefold: (1) Develop and utilize facile polymerization methods that allow for the synthesis of functional polymers with a wide range of properties, (2) understand the self-assembly properties of polymers and/or polymer grafted nanoparticles, and (3) combine (1) and (2) to tune any aspect of the PNCs, allowing for complete control over properties (e.g., dielectric constant, electrical conductivity) for a variety of energy applications.

In the short term, I envision utilizing the polymer synthesis technique I developed in my postdoctoral work, which allows us to easily create polyethers with a diverse range of functionalities and architectures. I will apply these polymers to develop an understanding of how different brush structures (e.g., block, graft, hyperbranched) affect the dispersion of nanoparticles in a polymer matrix, which affects the overall nanocomposite properties. I would also like to use polyether-grafted nanoparticles in polymer electrolytes for battery applications.  In this case, polyethers are a great choice as their dielectric properties can be tuned through the pendant group and grafting high dielectric polyether copolymers to the nanoparticles should further enhance the ionic conductivity.

Longer term, I am interested in the self-assembly of polymers of different architectures for lithography. Currently, linear block-co-polymers which create lamellar morphologies are the industry standard, but they are reaching their limit in terms of feature size. By using the polymerization platform I developed in my postdoctoral work, we could access different morphologies (e.g., gyroidal), architectures (e.g., bottle brush), and combinations of monomer units (i.e., for high χ), which would allow us to achieve industrially coveted domain spacing (i.e. sub 10 nm). I am also interested in stimuli-responsive and hybrid materials for energy applications. Creating materials for advanced applications necessitates individual components to act synergistically to achieve the target property set. Combining conducting polymers with metal and/or semiconducting nanoparticles in a rational way would allow us to make improved materials for energy harvesting applications (e.g., solar cells, thermoelectric generators).

Research Background:

Research Experience

Throughout my academic career I have worked toward understanding and controlling the interactions between polymers and nanoparticles. As an undergraduate and master’s student in the Physics and Materials Science and Engineering departments at Drexel University, I utilized functional polymer crystals to create Janus magnetic nanoparticles that could be co-assembled with other nanoparticle types to create hybrid nanomaterials. As a Ph.D. student in the Chemical and Biomolecular Engineering department at the University of Pennsylvania, I began working with polymer-grafted gold nanorods, which have unique optical properties due to their anisotropic shape. I designed methods to assemble gold nanorods permanently or reversibly through chemical (e.g., using peptides) or temperature (e.g., using DNA) responsive triggers, which allowed me to control optical properties of polymer films. I wanted to apply these ideas to other anisotropic particles and other matrices, which led me to work with both experimentalists and theorists in other fields. In this way, I have had many fruitful collaborations across campus (materials science, physics, chemistry) and across the world (Kyoto University (Japan), CNRS (France)). The collaborations led me to want to explore more diverse material systems; to do this, I felt I needed to increase my synthetic toolkit. As such, I joined a polymer chemistry laboratory in the Chemical Engineering department at the University of Texas at Austin. Here, I have learned various polymerization techniques such as anionic polymerization and radical polymerization. I have also developed a new facile polymerization method that has allowed us to synthesize unique, functional polymers at controlled molecular weights. I remain interested in polymer nanocomposites and I am currently using the polymerization platform I developed to create new nanocomposite materials.

Past Research Projects

Postdoctoral Project: “A New, Facile Approach for Epoxide Polymerizations Utilizing Organoaluminum Initiators” Supervised by Prof. Nathaniel A. Lynd in the Chemical Engineering Department at the University of Texas at Austin, 2016-Present   

International Research Fellow Project: “Probing the Interaction of Gold Nanorods and Organic Semiconductors” Supervised by Drs. Patrice Rannou, Brigitte Pépin-Donat, and Didier Gasparutto in INAC at CNRS in Grenoble, France, Summer-Fall 2013

NSF-EAPSI Fellow Project: “ATRP Initiated from Nanorod Surfaces” Supervised by Prof. Kohji Ohno in the Institute for Chemical Research at Kyoto University, Japan, Summer 2012

 Ph.D. Thesis: “Surface Chemistry Mediated Assembly of Polymer-Grafted Nanorods in Solution and Polymer Matrices” Supervised by Prof. Russell J. Composto in the Chemical and Biomolecular Engineering Department at the University of Pennsylvania, 2009-2015

 M.S. Thesis: “Polymer Templated Janus Magnetic Nanoparticles” Supervised by Prof. Christopher Y. Li in the Materials Science and Engineering Department at Drexel University, 2007-2009

 

Funded Proposals

NSF EAPSI Fellowship

Labex-ARCANE Fellowship

NBIC International Research Fellowship

Selected Publications

Robert C. Ferrier, Jr.^†, Jennifer Imbrogno^†, Christina G. Rodriguez^†, Malgorzata Chwatko, Paul W. Meyer, Nathaniel A. Lynd, Four-fold Increase in Epoxide Polymerization Rate with Change of Alkyl-substitution on mono-µ-oxo-dialuminum Initiators, Polymer Chemistry, 2017 (in press). † equal contribution

Christina G. Rodriguez^†, Robert C. Ferrier, Jr.^†, Alysha Helenic, Nathaniel A. Lynd, Ring Opening Polymerization of Epoxides: Facile Pathway to Functional Polyethers via a Versatile Organoaluminum Initiator, Macromolecules, 2017, 50 (8), pp 3121 – 3130. † equal contribution

Robert C. Ferrier, Jr. ^†, Jason Koski^†, Robert A. Riggleman, Russell J. Composto, Engineering the Assembly of Gold Nanorods in Polymer Matrices, Macromolecules, 2016, 49 (3), pp 1002-1015 † equal contribution

Elaine Lee^†, Yu Xia^†, Robert C. Ferrier, Jr. ^†, Hye-Na Kim, Mohamed A. Gharbi, Kathleen J. Stebe, Randall D. Kamien, Russell J. Composto, Shu Yang. Fine Golden Rings: A Tunable Surface Plasmon Resonance from Liquid Crystal Assembled Nanorods. Advanced Materials, 2016, 28, pp 2731-2736 †equal contribution

Robert C. Ferrier, Jr., Yun Huang, Kohji Ohno, Russell J. Composto. Dispersion of Polymer Grafted, Mesoscopic, Iron-oxide Rods in Polymer Matrices. Soft Matter, 2016, 12, pp 2550-2556

Robert C. Ferrier, Jr., Guillaume Gines, Didier Gasparutto, Brigitte Pépin-Donat, Patrice Rannou, Russell J. Composto. Tuning Optical Properties of Functionalized Gold Nanorods through Controlled Interactions with Organic Semiconductors. Journal of Physical Chemistry C, 2015, 119 (31), pp 17899-17909

Robert C. Ferrier, Jr., Hyun-Su Lee, Michael J. A. Hore, Matthew Caporizzo, David M. Eckmann, Russell J. Composto. Gold Nanorod Linking to Control Plasmonic Properties in Solution and Polymer Nanocomposites. Langmuir, 2014, 30 (7), pp 1906–1914

Teaching Interests:

Teaching and Mentoring Experience

For two years at the University of Pennsylvania, I was a teaching assistant (TA) and guest lecturer for the undergraduate class Soft Matter in the Materials Science department. As a TA, I prepared exam and homework questions, graded exams and homework, and helped determine the final curve and final grades.  I participated in several teaching workshops that helped expose me to a variety of different teaching styles. I also had one of my lectures evaluated to help me understand my strengths and weaknesses as a lecturer. Finally, mentorship is extremely important to me and I take it very seriously. I have been extremely lucky to have been able to nurture the scientific minds of a number of REU students, undergraduate senior design students, and graduate students during my Ph.D. and postdoctoral careers. Continuing to be a good mentor is something I look forward to when I become faculty.

Teaching Interests

I have an academic background that spans four different disciplines (chemistry, physics, materials science, and chemical engineering) so I would be suited to teach a wide variety of courses. Courses of particular interest would be: polymer physics, soft matter, polymer chemistry, and thermodynamics.