Understanding and Controlling the Self‐Folding Behavior of Poly (N‐Isopropylacrylamide) Microgel‐Based Devices

Poly(N-isopropylacrylamide) (pNIPAm) microgel-based materials can be fabricated that self-fold into three-dimensional structures in response to changes in the environmental humidity. The materials are composed of a semi-rigid polymer substrate coated with a thin layer of Au; the Au layer is subsequently coated with a pNIPAm-based microgel layer and finally covered with a solution of polydiallyldimethylammonium chloride (pDADMAC). The pDADMAC layer contracts upon drying causing the material to deform (typically bending); this deformation is completely reversible over many cycles as the environmental humidity is systematically varied. Here, by varying the size and aspect ratio of the polymer substrate, it is possible to develop a set of empirical rules that can be applied to predict the material's self-folding behavior. From these rules, materials that self-fold from two-dimensional, flat objects into discrete three-dimensional structures, which are fully capable of unfolding and folding multiple times in response to humidity, are designed.

[1]  Genaro Zavala,et al.  Mechanism of and Defect Formation in the Self-Assembly of Polymeric Polycation−Montmorillonite Ultrathin Films , 1997 .

[2]  R. Hayward,et al.  Designing Responsive Buckled Surfaces by Halftone Gel Lithography , 2012, Science.

[3]  Justin R. Kumpfer,et al.  Thermo-, photo-, and chemo-responsive shape-memory properties from photo-cross-linked metallo-supramolecular polymers. , 2011, Journal of the American Chemical Society.

[4]  Robert Langer,et al.  Bio-Inspired Polymer Composite Actuator and Generator Driven by Water Gradients , 2013, Science.

[5]  M. Carter,et al.  A "paint-on" protocol for the facile assembly of uniform microgel coatings for color tunable etalon fabrication. , 2011, ACS applied materials & interfaces.

[6]  David H Gracias,et al.  Three-dimensional fabrication at small size scales. , 2010, Small.

[7]  Elisabeth Smela,et al.  Edge effects determine the direction of bilayer bending. , 2011, Nano letters.

[8]  Keiji Fujimoto,et al.  Hydrogel microspheres III. Temperature-dependent adsorption of proteins on poly-N-isopropylacrylamide hydrogel microspheres , 1992 .

[9]  Malav S. Desai,et al.  Light-controlled graphene-elastin composite hydrogel actuators. , 2013, Nano letters.

[10]  Molla R. Islam,et al.  Polymer-based muscle expansion and contraction. , 2013, Angewandte Chemie.

[11]  Ik Su Chun,et al.  Geometry effect on the strain-induced self-rolling of semiconductor membranes. , 2010, Nano letters.

[12]  L. Andrew Lyon,et al.  Optical and Acoustic Studies of pH-Dependent Swelling in Microgel Thin Films , 2004 .

[13]  K. Gall,et al.  Shape-memory polymer networks with Fe3O4 nanoparticles for remote activation , 2009 .

[14]  Eugene M. Terentjev,et al.  Photomechanical actuation in polymer–nanotube composites , 2005, Nature materials.

[15]  E. Kumacheva,et al.  Multiple shape transformations of composite hydrogel sheets. , 2013, Journal of the American Chemical Society.

[16]  Molla R. Islam,et al.  Penetration of Polyelectrolytes into Charged Poly(N-isopropylacrylamide) Microgel Layers Confined between Two Surfaces , 2013 .

[17]  M. Serpe,et al.  Reflection Order Selectivity of Color‐Tunable Poly(N‐isopropylacrylamide) Microgel Based Etalons , 2011, Advanced materials.

[18]  Zhibing Hu,et al.  Synthesis and Application of Modulated Polymer Gels , 1995, Science.

[19]  Liesbet Lagae,et al.  Nanoscale origami for 3D optics. , 2011, Small.

[20]  Jeong-Hyun Cho,et al.  Three dimensional nanofabrication using surface forces. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[21]  Kai Liu,et al.  Giant-amplitude, high-work density microactuators with phase transition activated nanolayer bimorphs. , 2012, Nano letters.

[22]  Jindřich Kopeček,et al.  Polymer chemistry: Swell gels , 2002, Nature.

[23]  Wendelin Jan Stark,et al.  Crosslinking metal nanoparticles into the polymer backbone of hydrogels enables preparation of soft, magnetic field-driven actuators with muscle-like flexibility. , 2009, Small.

[24]  T. Okano,et al.  Comb-type grafted hydrogels with rapid deswelling response to temperature changes , 1995, Nature.

[25]  Leonid Ionov,et al.  Hierarchical Multi‐Step Folding of Polymer Bilayers , 2013 .

[26]  J. Schlenoff,et al.  Polyelectrolyte Multilayers with Reversible Thermal Responsivity , 2005 .

[27]  Chi Wu,et al.  Laser Light Scattering Study of the Phase Transition of Poly(N-isopropylacrylamide) in Water. 1. Single Chain , 1995 .