Department of Chemistry

Polymers, Materials, and Nanoscience

Research ImageMany challenging problems in the modern science and technology are related to preparation, properties, and utilization of novel functional materials. The polymer chemistry and the chemical microelectronics programs represent parts of the multidisciplinary effort in this field. The many-pronged approach includes: synthesis and molecular characterization of well-defined block and graft copolymers; preparation of new engineering thermoplastics and liquid crystalline materials; synthesis, modification and processing of polymers in super-critical carbon dioxide; chemical design of hybrid polymers for catalysis and photoredox activity, polymers for microelectronics applications including 193 nm and 157 nm photoresists and low-k dielectrics, and defined microstructures.

Chemical microelectronics is focused on preparation of organic and inorganic electronic materials; microscopic patterning of thin films using novel techniques, plasma, ion beam, laser beam, etc.; kinetics of etching and film formation; characterization of mechanical, electronic, and optical properties; spatially resolved chemical analysis of surfaces, interfaces, and thin films and microstructures. A broad variety of expertise includes visualization and probing of submicrometer surface structures by scanning probe microscopy, characterization of polymer dynamics by NMR techniques and light scattering, measurement of molecular conductivity, and analytical as well as computational and numerical methods in polymers.

 

Recent Research Highlights

Lubrication by Polyelectrolyte Brushes

Published in Macromolecules, Professor Michael Rubinstein, in collaboration with Ekaterina Zhulina with the Institute of Macromolecular Compounds, Russian Academy of Sciences in Saint Petersburg, describe the development of a scaling model relating the friction forces between two polyelectrolyte brushes sliding over each other to the separation between grafted surfaces, number of monomers and charges per chain, grafting density of chains, and solvent quality. They demonstrate that the lateral force between brushes increases upon compression, but to a lesser extent than the normal force.

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The shear stress at larger separations is due to solvent slip layer friction. The thickness of this slip layer sharply decreases at distances on the order of undeformed brush thickness. The corresponding effective viscosity of the layer sharply increases from the solvent viscosity to a much higher value, but this increase is smaller than the jump of the normal force resulting in the drop of the friction coefficient. At stronger compression the group members predict the second sharp increase of the shear stress corresponding to interpenetration of the chains from the opposite brushes. In this regime the velocity-dependent friction coefficient between two partially interpenetrating polyelectrolyte brushes does not depend on the distance between substrates because both normal and shear forces are reciprocally proportional to the plate separation. Although lateral forces between polyelectrolyte brushes are larger than between bare surfaces, the enhancement of normal forces between opposing polyelectrolyte brushes with respect to normal forces between bare charged surfaces is much stronger resulting in lower friction coefficient. The model quantitatively demonstrates how polyelectrolyte brushes provide more effective lubrication than bare charged surfaces or neutral brushes.

 

Shapeshifting

Biological systems have the ability to program reversible shape changes in response to cues from their environment. While a variety of adaptive and stimuli-responsive materials like hydrogels, liquid crystalline elastomers, and shape memory materials have been developed, mimicking programmable behavior in a reversible way remains elusive.

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Work published in Macromolecules by the Sheiko and Ashby groups, in collaboration with the University of Connecticut, Brookhaven and Oak Ridge National Labs, has shown that semi-crystalline elastomers may undergo reversible switching between well-defined shapes without applying any external forces. This behavior stems from the correlated interplay between a crystalline scaffold and a network of chemical crosslinks, each capable of encoding a distinct shape. The universal mechanism of reversible shapeshifting affords interesting opportunities for minimally invasive surgery, shape programmable biomedical implants, surgical sealants, and hands-free packaging.

 

Representative Publications

Hopping Diffusion of Nanoparticles in Polymer Matrices. Li-Heng Cai Sergey Panyukov, and Michael Rubinstein. Macromolecules, 2015, 48 (3), pp 847–862.

Doubling Absorption in Nanowire Solar Cells with Dielectric Shell Optical Antennas. Kim, Sun-Kyung; Zhang, Xing; Hill, David J.; Song, Kyung-Deok; Park, Jin-Sung; Park, Hong-Gyu; Cahoon, James F.. NANO LETTERS, 15 (1):753-758; 10.1021/nl504462e JAN 2015.

Continuous Liquid Interface Production of 3D Objects. John R. Tumbleston, David Shirvanyants, Nikita Ermoshkin, Rima Janusziewicz, Ashley R. Johnson, David Kelly, Kai Chen, Robert Pinschmidt, Jason P. Rolland, Alexander Ermoshkin, Edward T. Samulski, Joseph M. DeSimone. Science 20 March 2015, Vol. 347 no. 6228 pp. 1349-1352.

The Role of Temperature in Forming Sol–Gel Biocomposites Containing Polydopamine. Jason Christopher Dyke, Huamin Hu, Dong Joon Lee, Ching-Chang Ko, and Wei You. J. Mater. Chem. B, 2014,2, 7704-7711.

Lubrication by Polyelectrolyte Brushes. Ekaterina B. Zhulina and Michael Rubinstein. Macromolecules, 2014, 47 (16), pp 5825–5838.

Shapeshifting: Reversible Shape Memory in Semicrystalline Elastomers. Jing Zhou, Sara A. Turner, Sarah M. Brosnan, Qiaoxi Li, Jan-Michael Y. Carrillo, Dmytro Nykypanchuk, Oleg Gang, Valerie S. Ashby, Andrey V. Dobrynin, and Sergei S. Sheiko. Nature Methods 11, 959–965 (2014).

Waveguide Scattering Microscopy for Dark-Field Imaging and Spectroscopy of Photonic Nanostructures. David J. Hill , Christopher W. Pinion , Joseph D. Christesen , and James F. Cahoon. ACS Photonics, 2014, 1 (8), pp 725–731.

Switchable Micropatterned Surface Topographies Mediated by Reversible Shape Memory. Sara A. Turner, Jing Zhou, Sergei S. Sheiko, and Valerie Sheares Ashby. ACS Appl. Mater. Interfaces, 2014, 6 (11), pp 8017–8021.

Particle Replication in Nonwetting Templates Nanoparticles with Tumor Selective Alkyl Silyl Ether Docetaxel Prodrug Reduces Toxicity. Kevin S. Chu, Mathew C. Finniss, Allison N. Schorzman, Jennifer L. Kuijer, J. Christopher Luft, Charles J. Bowerman, Mary E. Napier, Zishan A. Haroon, William C. Zamboni. Nano Lett., 2014, 14 (3), pp 1472–1476.

Controlling Molecular Weight of a High Efficiency Donor-Acceptor Conjugated Polymer and Understanding Its Significant Impact on Photovoltaic Properties. Wentao Li, Liqiang Yang, John R. Tumbleston, Liang Yan, Harald Ade, and Wei You. Adv. Mat., First published online, 14 MAR 2014, DOI: 10.1002/adma.201305251.