Self-Healing Four-Dimensional Printing with an Ultraviolet Curable Double-Network Shape Memory Polymer System.

Four-dimensional (4D) printing that enables 3D printed structures to change configurations over time has gained great attention because of its exciting potential in various applications. Among all the 4D printing materials, shape memory polymers (SMPs) possess higher stiffness and faster response rate and therefore are considered as one of most promising materials for 4D printing. However, most of the SMP-based 4D printing materials are (meth)acrylate thermosets which have permanently cross-linked covalent networks and cannot be repaired if any damage occurs. To address the unrepairable nature of SMP-based 4D printing materials, this paper reports a double-network self-healing SMP (SH-SMP) system for high-resolution self-healing 4D printing. In the SH-SMP system, the semicrystalline linear polymer polycaprolactone (PCL) is incorporated into a methacrylate-based SMP system which has good compatibility with the digital light processing-based 3D printing technology and can be used to fabricate complex 4D printing structures with high resolution (up to 30 μm). The PCL linear polymer imparts the self-healing ability to the 4D printing structures, and the mechanical properties of a damaged structure can be recovered to more than 90% after adding more than 20 wt % of PCL into the SH-SMP system. We investigated the effects of PCL concentration on the thermomechanical behavior, viscosity, and the self-healing capability of the SH-SMP system and performed the computational fluid dynamics simulations to study the effect of SH-SMP solution's viscosity on the 3D printing process. Finally, we demonstrated the self-healing 4D printing application examples to show the merits of the SH-SMP system.

[1]  Yong Liu,et al.  3D printing of smart materials: A review on recent progresses in 4D printing , 2015 .

[2]  Marinella Levi,et al.  4D printed thermally activated self-healing and shape memory polycaprolactone-based polymers , 2018 .

[3]  Shannon E Bakarich,et al.  4D Printing with Mechanically Robust, Thermally Actuating Hydrogels. , 2015, Macromolecular rapid communications.

[4]  Ole Hansen,et al.  Electro-thermally actuated microgrippers with integrated force-feedback , 2005 .

[5]  Martin L. Dunn,et al.  Thermomechanical behavior of shape memory elastomeric composites , 2012 .

[6]  Xin Lan,et al.  Fiber reinforced shape-memory polymer composite and its application in a deployable hinge , 2009 .

[7]  Qi Ge,et al.  Active materials by four-dimension printing , 2013 .

[8]  Xuanhe Zhao,et al.  Cephalopod-inspired design of electro-mechano-chemically responsive elastomers for on-demand fluorescent patterning , 2014, Nature Communications.

[9]  Hye Rin Kwag,et al.  Stimuli-responsive theragrippers for chemomechanical controlled release. , 2014, Angewandte Chemie.

[10]  Skylar Tibbits,et al.  4D Printing: Multi‐Material Shape Change , 2014 .

[11]  Dong Yan,et al.  Pattern Transformation of Heat-Shrinkable Polymer by Three-Dimensional (3D) Printing Technique , 2015, Scientific Reports.

[12]  Qi Ge,et al.  Reduced time as a unified parameter determining fixity and free recovery of shape memory polymers , 2014, Nature Communications.

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

[14]  Lang Xia,et al.  4D printing of polymeric materials for tissue and organ regeneration. , 2017, Materials today.

[15]  G. Spinks,et al.  4D Printing of Reversible Shape Morphing Hydrogel Structures , 2017 .

[16]  Amir Hosein Sakhaei,et al.  Highly stretchable hydrogels for UV curing based high-resolution multimaterial 3D printing. , 2018, Journal of materials chemistry. B.

[17]  Martin M. Mikulas,et al.  Carbon Fiber Reinforced Shape Memory Polymer Composites , 2000 .

[18]  Hye Rin Kwag,et al.  Self-Folding Thermo-Magnetically Responsive Soft Microgrippers , 2015, ACS applied materials & interfaces.

[19]  Qi Ge,et al.  Thermomechanics of printed anisotropic shape memory elastomeric composites , 2016 .

[20]  M. Layani,et al.  3D Printing of Shape Memory Polymers for Flexible Electronic Devices , 2016, Advanced materials.

[21]  Zeyun Xiao,et al.  Three-Dimensional Printing of pH-Responsive and Functional Polymers on an Affordable Desktop Printer. , 2016, ACS applied materials & interfaces.

[22]  Xiaofan Luo,et al.  Linear/network poly(ε-caprolactone) blends exhibiting shape memory assisted self-healing (SMASH). , 2011, ACS applied materials & interfaces.

[23]  D. Rus,et al.  Design, fabrication and control of soft robots , 2015, Nature.

[24]  Amir Hosein Sakhaei,et al.  Highly Stretchable and UV Curable Elastomers for Digital Light Processing Based 3D Printing , 2017, Advanced materials.

[25]  Jiangtao Wu,et al.  3D Printing of Highly Stretchable, Shape-Memory, and Self-Healing Elastomer toward Novel 4D Printing. , 2018, ACS applied materials & interfaces.

[26]  Shir Shapira,et al.  4D Printing of Shape Memory-Based Personalized Endoluminal Medical Devices. , 2017, Macromolecular rapid communications.

[27]  M. Wagner,et al.  Development of a polymer stent with shape memory effect as a drug delivery system , 2003, Journal of materials science. Materials in medicine.

[28]  Ramesh Raskar,et al.  Active Printed Materials for Complex Self-Evolving Deformations , 2014, Scientific Reports.

[29]  Ningbin Zhang,et al.  Fast‐Response, Stiffness‐Tunable Soft Actuator by Hybrid Multimaterial 3D Printing , 2019, Advanced Functional Materials.

[30]  Robin Shandas,et al.  Unconstrained recovery characterization of shape-memory polymer networks for cardiovascular applications. , 2007, Biomaterials.

[31]  M. Dunn,et al.  Photo-origami—Bending and folding polymers with light , 2012 .

[32]  Wei-Hsin Liao,et al.  Triple shape memory polymers by 4D printing , 2018 .

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

[34]  Chao Yuan,et al.  3D Printed Reversible Shape Changing Components with Stimuli Responsive Materials , 2016, Scientific Reports.

[35]  R. Langer,et al.  Light-induced shape-memory polymers , 2005, Nature.

[36]  Leonid Ionov,et al.  4D Biofabrication Using Shape‐Morphing Hydrogels , 2017, Advanced materials.

[37]  W. Benett,et al.  Fabrication and in vitro deployment of a laser-activated shape memory polymer vascular stent , 2007, Biomedical engineering online.

[38]  Martin L. Dunn,et al.  Photomechanics of light-activated polymers , 2009 .

[39]  Choon Chiang Foo,et al.  Stretchable, Transparent, Ionic Conductors , 2013, Science.

[40]  Xiaofan Luo,et al.  Shape Memory Assisted Self-Healing Coating. , 2013, ACS macro letters.

[41]  Robert J. Wood,et al.  A 3D-printed, functionally graded soft robot powered by combustion , 2015, Science.

[42]  Martin L. Dunn,et al.  Active origami by 4D printing , 2014 .

[43]  Jun Ni,et al.  A review of 4D printing , 2017 .

[44]  D. Hutmacher,et al.  The return of a forgotten polymer : Polycaprolactone in the 21st century , 2009 .

[45]  Robin Shandas,et al.  Effects of thermal rates on the thermomechanical behaviors of amorphous shape memory polymers , 2010 .

[46]  John R. Tumbleston,et al.  Continuous liquid interface production of 3D objects , 2015, Science.

[47]  T. Xie.  Tunable polymer multi-shape memory effect , 2010, Nature.

[48]  Amir Hosein Sakhaei,et al.  Multimaterial 4D Printing with Tailorable Shape Memory Polymers , 2016, Scientific Reports.

[49]  Qi Ge,et al.  Prediction of temperature-dependent free recovery behaviors of amorphous shape memory polymers , 2012 .

[50]  Rongrong Zhang,et al.  4D Printing of Robust Hydrogels Consisted of Agarose Nanofibers and Polyacrylamide. , 2018, ACS macro letters.

[51]  A. Lendlein,et al.  Shape-memory polymers , 2002 .

[52]  Robert J. Wood,et al.  An integrated design and fabrication strategy for entirely soft, autonomous robots , 2016, Nature.

[53]  J. Lewis,et al.  Printing soft matter in three dimensions , 2016, Nature.