Surface Patterning of Hydrogels for Programmable and Complex Shape Deformations by Ion Inkjet Printing

Convenient patterning and precisely programmable shape deformations are crucial for the practical applications of shape deformable hydrogels. Here, a facile and versatile computer-assisted ion inkjet printing technique is described that enables the direct printing of batched, very complicated patterns, especially those with well-defined, programmable variation in cross-linking densities, on one or both surfaces of a large-sized hydrogel sample. A mechanically strong hydrogel containing poly(sodium acrylate) is first prepared, and then digital patterns are printed onto the hydrogel surfaces by using a commercial inkjet printer and an aqueous ferric solution. The complexation between the polyelectrolyte and ferric ions increases the cross-linking density of the printed regions, and hence the gel sample can undergo shape deformation upon swelling/deswelling. The deformation rates and degrees of the hydrogels can be conveniently adjusted by changing the printing times or the different/gradient grayscale distribution of designed patterns. By printing appropriate patterns on one or both surfaces of the hydrogel sheets, many complex 3D shapes are obtained from shape deformations upon swelling/deswelling, such as cylindrical shell and forsythia flower (patterns on one surface), ding (patterns on both surfaces), blooming flower (different/gradient grayscale distributive patterns on one surface), and non-Euclidean plates (different/gradient grayscale distributive patterns on both surfaces).

[1]  L. Chu,et al.  Smart Hydrogels with Inhomogeneous Structures Assembled Using Nanoclay-Cross-Linked Hydrogel Subunits as Building Blocks. , 2016, ACS applied materials & interfaces.

[2]  L. Mahadevan,et al.  The shape of a long leaf , 2009, Proceedings of the National Academy of Sciences.

[3]  Terence G. Henares,et al.  Paper-based inkjet-printed microfluidic analytical devices. , 2015, Angewandte Chemie.

[4]  Huiliang Wang,et al.  Rheological Behavior of Tough PVP-in Situ-PAAm Hydrogels Physically Cross-Linked by Cooperative Hydrogen Bonding , 2016 .

[5]  Bruce P. Lee,et al.  Novel Hydrogel Actuator Inspired by Reversible Mussel Adhesive Protein Chemistry , 2014, Advanced materials.

[6]  E. Palleau,et al.  Reversible patterning and actuation of hydrogels by electrically assisted ionoprinting , 2013, Nature Communications.

[7]  Leonid Ionov,et al.  Unusual and Superfast Temperature‐Triggered Actuators , 2015, Advanced materials.

[8]  P. Calvert Hydrogels for Soft Machines , 2009 .

[9]  M. Sasaki,et al.  Preparation of a novel composition-gradient thermosensitive gel , 2006 .

[10]  Haiyi Liang,et al.  Growth, geometry, and mechanics of a blooming lily , 2011, Proceedings of the National Academy of Sciences.

[11]  Y. Takashima,et al.  Expansion–contraction of photoresponsive artificial muscle regulated by host–guest interactions , 2012, Nature Communications.

[12]  Jizhou Song,et al.  Ultrafast Digital Printing toward 4D Shape Changing Materials , 2017, Advanced materials.

[13]  Ryan R. Kohlmeyer,et al.  Remote, local, and chemical programming of healable multishape memory polymer nanocomposites. , 2012, Nano letters.

[14]  André R Studart,et al.  Self-shaping composites with programmable bioinspired microstructures , 2013, Nature Communications.

[15]  Huiliang Wang,et al.  Facile Fabrication of Tough Hydrogels Physically Cross-Linked by Strong Cooperative Hydrogen Bonding , 2013 .

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

[17]  Leonid Ionov,et al.  Anisotropic Liquid Microcapsules from Biomimetic Self-Folding Polymer Films. , 2015, ACS applied materials & interfaces.

[18]  Xin Peng,et al.  Tough Hydrogels with Programmable and Complex Shape Deformations by Ion Dip‐Dyeing and Transfer Printing , 2016 .

[19]  Tiefeng Li,et al.  Supramolecular Lego Assembly Towards Three‐Dimensional Multi‐Responsive Hydrogels , 2014, Advanced materials.

[20]  J. Rogers,et al.  Deformable, Programmable, and Shape‐Memorizing Micro‐Optics , 2013 .

[21]  Karl Crowley,et al.  An aqueous ammonia sensor based on an inkjet-printed polyaniline nanoparticle-modified electrode. , 2008, The Analyst.

[22]  Chia-Hung Chen,et al.  Gradient Porous Elastic Hydrogels with Shape‐Memory Property and Anisotropic Responses for Programmable Locomotion , 2015 .

[23]  E. Sharon,et al.  Shaping of Elastic Sheets by Prescription of Non-Euclidean Metrics , 2007, Science.

[24]  Yihu Song,et al.  Metal-Coordination Complexes Mediated Physical Hydrogels with High Toughness, Stick–Slip Tearing Behavior, and Good Processability , 2016 .

[25]  Yang Liu,et al.  Programmable responsive shaping behavior induced by visible multi-dimensional gradients of magnetic nanoparticles , 2012 .

[26]  Wei Lu,et al.  A Multiresponsive Anisotropic Hydrogel with Macroscopic 3D Complex Deformations , 2016 .

[27]  R. Vaia,et al.  Shape‐Reprogrammable Polymers: Encoding, Erasing, and Re‐Encoding , 2014, Advanced materials.

[28]  D. Henderson,et al.  Crocheting the hyperbolic plane , 2001 .

[29]  Bruce P. Lee,et al.  Effect of metal ion type on the movement of hydrogel actuator based on catechol-metal ion coordination chemistry , 2016 .

[30]  M. Jamal,et al.  Differentially photo-crosslinked polymers enable self-assembling microfluidics. , 2011, Nature communications.

[31]  R. Kupferman,et al.  Geometry and Mechanics in the Opening of Chiral Seed Pods , 2011, Science.

[32]  Elisabetta A. Matsumoto,et al.  Biomimetic 4D printing. , 2016, Nature materials.

[33]  Liang-Yin Chu,et al.  Poly(N‐isopropylacrylamide)‐Clay Nanocomposite Hydrogels with Responsive Bending Property as Temperature‐Controlled Manipulators , 2015 .

[34]  R. Kupferman,et al.  Elastic theory of unconstrained non-Euclidean plates , 2008, 0810.2411.

[35]  Akira Harada,et al.  Redox-generated mechanical motion of a supramolecular polymeric actuator based on host-guest interactions. , 2013, Angewandte Chemie.

[36]  R. Hayward,et al.  Thermally responsive rolling of thin gel strips with discrete variations in swelling , 2012 .

[37]  Leonid Ionov,et al.  Hydrogel-based actuators: possibilities and limitations , 2014 .

[38]  George M. Whitesides,et al.  Spontaneous formation of ordered structures in thin films of metals supported on an elastomeric polymer , 1998, Nature.

[39]  Bruce P. Lee,et al.  Modulating the movement of hydrogel actuator based on catechol–iron ion coordination chemistry , 2015 .

[40]  Hwan Chul Jeon,et al.  Controlled origami folding of hydrogel bilayers with sustained reversibility for robust microcarriers. , 2012, Angewandte Chemie.

[41]  L. Chu,et al.  Hydrogel Walkers with Electro-Driven Motility for Cargo Transport , 2015, Scientific Reports.

[42]  Xuanhe Zhao,et al.  Hydraulic hydrogel actuators and robots optically and sonically camouflaged in water , 2017, Nature Communications.

[43]  Brian Derby,et al.  Printing and Prototyping of Tissues and Scaffolds , 2012, Science.

[44]  Xiaolong Wang,et al.  Molecularly Engineered Dual‐Crosslinked Hydrogel with Ultrahigh Mechanical Strength, Toughness, and Good Self‐Recovery , 2015, Advanced materials.

[45]  W. Hong,et al.  Programmed planar-to-helical shape transformations of composite hydrogels with bioinspired layered fibrous structures. , 2016, Journal of materials chemistry. B.

[46]  Xiao Lin,et al.  Hydrophobic association mediated physical hydrogels with high strength and healing ability , 2016 .

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

[48]  R. Yoshida,et al.  Self‐Walking Gel , 2007 .

[49]  Stephen Z. D. Cheng,et al.  Three-dimensional actuators transformed from the programmed two-dimensional structures via bending, twisting and folding mechanisms , 2011 .

[50]  Michiya Matsusaki,et al.  Fabrication of Temperature‐Responsive Bending Hydrogels with a Nanostructured Gradient , 2008 .

[51]  Qiang Zhao,et al.  An instant multi-responsive porous polymer actuator driven by solvent molecule sorption , 2014, Nature Communications.

[52]  J. Greener,et al.  Three-dimensional shape transformations of hydrogel sheets induced by small-scale modulation of internal stresses , 2013, Nature Communications.

[53]  E. Sharon,et al.  The mechanics of non-Euclidean plates , 2010 .

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