4D printing of shape memory polylactic acid (PLA)

Abstract Additive manufacturing has attracted much attention in the last decade as a principal growing sector of complex manufacturing. Precise layer-by-layer patterning of materials gives rise to novel designs and fabrication strategies that were previously not possible to realize with conventional techniques. Using suitable materials and organized variation in the printing settings, parts with time-dependent shapes that can be tuned through environmental stimuli can be realized. Given that these parts can either change their shape over time to a pre-programmed three-dimensional shape or revert to an initial design, this process has become referred to as four-dimensional (4D) printing. In this regard, the commonly-used polylactic acid (PLA) polymer has been recognized as a compelling material candidate for 4D printing as it is a biobased polymer with great shape memory behavior that can be employed in the design and manufacturing of a broad range of smart products. In this review, we investigate the material properties and shape memory behavior of PLA polymer in the first section. Then, we discuss the potential of PLA for 4D printing, including the principles underlying the strategy for PLA-based printing of self-folding structures. The resulting materials exhibit response to environmental stimulus as well as temperature, magnetic field, or light. We additionally discuss the impact of geometrical design and printing conditions on the functionality of the final printed products.

[1]  Ye Li,et al.  Development and kinetic evaluation of a low-cost temperature-sensitive shape memory polymer for 4-dimensional printing , 2020 .

[2]  Yanju Liu,et al.  4D Printing Auxetic Metamaterials with Tunable, Programmable, and Reconfigurable Mechanical Properties , 2020, Advanced Functional Materials.

[3]  A. Lendlein,et al.  Multifunctional Shape‐Memory Polymers , 2010, Advanced materials.

[4]  Skylar Tibbits,et al.  4D Printing and Universal Transformation , 2014, Proceedings of the 34th Annual Conference of the Association for Computer Aided Design in Architecture (ACADIA).

[5]  E. Pei,et al.  4D printing: processability and measurement of recovery force in shape memory polymers , 2016, The International Journal of Advanced Manufacturing Technology.

[6]  A. Chiralt,et al.  Combination of Poly(lactic) Acid and Starch for Biodegradable Food Packaging , 2017, Materials.

[7]  Jie Song,et al.  Polylactic acid (PLA)-based shape-memory materials for biomedical applications , 2015 .

[8]  H. Meng,et al.  A review of stimuli-responsive shape memory polymer composites , 2013 .

[9]  Tomy J. Gutiérrez,et al.  Nanocomposite biomaterials made by 3D printing: Achievements and challenges , 2021 .

[10]  L. Zsidai,et al.  Accuracy investigation of 3D printed PLA with various process parameters and different colors , 2021, Materials Today: Proceedings.

[11]  Xiang 'Anthony' Chen,et al.  Thermorph: Democratizing 4D Printing of Self-Folding Materials and Interfaces , 2018, CHI.

[12]  R. M. Filho,et al.  Synthesis and Characterizations of Poly (Lactic Acid) by Ring-Opening Polymerization for Biomedical Applications , 2014 .

[13]  S. Ray,et al.  Organically modified layered titanate: A new nanofiller to improve the performance of biodegradable polylactide , 2004 .

[14]  Vasif Hasirci,et al.  3D and 4D Printing of Polymers for Tissue Engineering Applications , 2019, Front. Bioeng. Biotechnol..

[15]  Amir A Zadpoor,et al.  Programming 2D/3D shape-shifting with hobbyist 3D printers† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7mh00269f , 2017, Materials horizons.

[16]  J. E. Mark Some novel polymeric nanocomposites. , 2006, Accounts of chemical research.

[17]  Yu-Zhong Wang,et al.  4D printing of shape memory aliphatic copolyester via UV-assisted FDM strategy for medical protective devices , 2020 .

[18]  Arndt F Schilling,et al.  Polylactides in additive biomanufacturing. , 2016, Advanced drug delivery reviews.

[19]  Manjusri Misra,et al.  Perspective on Polylactic Acid (PLA) based Sustainable Materials for Durable Applications: Focus on Toughness and Heat Resistance , 2016 .

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

[21]  Ji Zhao,et al.  Influence of Layer Thickness, Raster Angle, Deformation Temperature and Recovery Temperature on the Shape-Memory Effect of 3D-Printed Polylactic Acid Samples , 2017, Materials.

[22]  Yuan Siang Lui,et al.  4D printing and stimuli-responsive materials in biomedical aspects. , 2019, Acta biomaterialia.

[23]  Liang Hou,et al.  Additive manufacturing and its societal impact: a literature review , 2013 .

[24]  Xuelian Wu,et al.  Advanced Shape Memory Technology to Reshape Product Design, Manufacturing and Recycling , 2014 .

[25]  Chao Yuan,et al.  Multi-shape active composites by 3D printing of digital shape memory polymers , 2016, Scientific Reports.

[26]  U. Schubert,et al.  Shape memory polymers: Past, present and future developments , 2015 .

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

[28]  Mohammad Haghighat Kish,et al.  Structure–property relationship for poly(lactic acid) (PLA) filaments: physical, thermomechanical and shape memory characterization , 2012, Journal of polymer research.

[29]  Han Ding,et al.  Review of mechanisms and deformation behaviors in 4D printing , 2019, The International Journal of Advanced Manufacturing Technology.

[30]  Mohammad Reza Saeb,et al.  Biodegradable polyester thin films and coatings in the line of fire: the time of polyhydroxyalkanoate (PHA)? , 2019, Progress in Organic Coatings.

[31]  F. Senatov,et al.  Mechanical properties and shape memory effect of 3D-printed PLA-based porous scaffolds. , 2016, Journal of the mechanical behavior of biomedical materials.

[32]  H. Khonakdar,et al.  In depth analysis of micro-mechanism of mechanical property alternations in PLA/EVA/clay nanocomposites: A combined theoretical and experimental approach , 2015 .

[33]  Wei Wang,et al.  Origami spring–inspired metamaterials and robots: An attempt at fully programmable robotics , 2020, Science progress.

[34]  Chih-Yuan Chang Study on the Correlation between Humidity and Material Strains in Separable Micro Humidity Sensor Design , 2017, Sensors.

[35]  R. P. John,et al.  An overview of the recent developments in polylactide (PLA) research. , 2010, Bioresource technology.

[36]  Sati N. Bhattacharya,et al.  Compatibility of biodegradable poly (lactic acid) (PLA) and poly (butylene succinate) (PBS) blends for packaging application , 2007 .

[37]  Barry Berman,et al.  3D printing: the new industrial revolution , 2012, IEEE Engineering Management Review.

[38]  Yanju Liu,et al.  4D printed anisotropic structures with tailored mechanical behaviors and shape memory effects , 2020 .

[39]  Y. Kimura,et al.  Chapter 1:PLA Synthesis. From the Monomer to the Polymer , 2014 .

[40]  Jack G. Zhou,et al.  Current status of 4D printing technology and the potential of light-reactive smart materials as 4D printable materials , 2016 .

[41]  S. Kim,et al.  Blending of poly(L-lactic acid) with poly(cis-1,4-isoprene) , 2000 .

[42]  Lin Xiao,et al.  Poly(Lactic Acid)-Based Biomaterials: Synthesis, Modification and Applications , 2012 .

[43]  A. Azizi,et al.  Investigation on the Functionality of Thermoresponsive Origami Structures , 2020, Advanced Engineering Materials.

[44]  Henry Brem,et al.  Polylactic acid (PLA) controlled delivery carriers for biomedical applications. , 2016, Advanced drug delivery reviews.

[45]  Wenqi Wang,et al.  Three-dimensional printing of complex structures: man made or toward nature? , 2014, ACS nano.

[46]  K. K. Patel,et al.  Future Prospects of shape memory polymer nano-composite and epoxy based shape memory polymer- A review , 2018 .

[47]  Bethany C Gross,et al.  Evaluation of 3D printing and its potential impact on biotechnology and the chemical sciences. , 2014, Analytical chemistry.

[48]  P. Ermanni,et al.  3D printing of multifunctional materials for sensing and actuation: Merging piezoelectricity with shape memory , 2020 .

[49]  M. Saeb,et al.  Unspoken aspects of chain shuttling reactions: Patterning the molecular landscape of olefin multi-block copolymers , 2017 .

[50]  S. Kang,et al.  Effects of Environmental Temperature and Humidity on the Geometry and Strength of Polycarbonate Specimens Prepared by Fused Filament Fabrication , 2020, Materials.

[51]  Yongjin Li,et al.  Toughening of polylactide by melt blending with a biodegradable poly(ether)urethane elastomer. , 2007, Macromolecular bioscience.

[52]  Suryani Dyah Astuti,et al.  Review of Polymeric Materials in 4D Printing Biomedical Applications , 2019, Polymers.

[53]  C. C. Wang,et al.  An overview of elastic polymeric shape memory materials for comfort fitting , 2017 .

[54]  Carmen M. González-Henríquez,et al.  Polymers for additive manufacturing and 4D-printing: Materials, methodologies, and biomedical applications , 2019, Progress in Polymer Science.

[55]  Wei Min Huang,et al.  Shape change/memory actuators based on shape memory materials , 2017 .

[56]  Ye Zhou,et al.  From 3D to 4D printing: approaches and typical applications , 2015, Journal of Mechanical Science and Technology.

[57]  Y. Inoue,et al.  Toughening of poly(L‐lactide) by melt blending with rubbers , 2009 .

[58]  Mahdi Bodaghi,et al.  Shape-Adaptive Metastructures with Variable Bandgap Regions by 4D Printing , 2020, Polymers.

[59]  A. Müller,et al.  Molecular Mobilities in Biodegradable Poly(dl-lactide)/Poly(ε-caprolactone) Blends , 2009 .

[60]  Chin I Lin,et al.  Synthesis and characterization of TPO–PLA copolymer and its behavior as compatibilizer for PLA/TPO blends , 2008 .

[61]  A. A. Zadpoor,et al.  Multi-material 3D printed mechanical metamaterials: Rational design of elastic properties through spatial distribution of hard and soft phases , 2018, Applied Physics Letters.

[62]  Tao Xi Wang,et al.  Heating-Responsive Shape-Memory Effect in Thermoplastic Polyurethanes with Low Melt-Flow Index , 2014 .

[63]  K. Shakesheff,et al.  Surface Analysis of Biodegradable Polymer Blends of Poly(sebacic anhydride) and Poly(dl-lactic acid) , 1996 .

[64]  Weiyi Zhou,et al.  Super tough poly(lactic acid) blends: a comprehensive review , 2020, RSC advances.

[65]  Jinsong Leng,et al.  Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications. , 2016, Tissue engineering. Part C, Methods.

[66]  C. S. Lin,et al.  Newly Developed Techniques on Polycondensation, Ring-Opening Polymerization and Polymer Modification: Focus on Poly(Lactic Acid) , 2016, Materials.

[67]  A. Akbarzadeh,et al.  3D printed architected polymeric sandwich panels: Energy absorption and structural performance , 2018, Composite Structures.

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

[69]  Wei Min Huang,et al.  Thermo/chemo-responsive shape memory effect in polymers: a sketch of working mechanisms, fundamentals and optimization , 2012, Journal of Polymer Research.

[70]  S. Ramakrishna,et al.  Characterization of three‐dimensional printed thermal‐stimulus polylactic acid‐hydroxyapatite‐based shape memory scaffolds , 2020 .

[71]  A. P. Valerga,et al.  Influence of PLA Filament Conditions on Characteristics of FDM Parts , 2018, Materials.

[72]  Annamaria Gisario,et al.  Metal additive manufacturing in the commercial aviation industry: A review , 2019, Journal of Manufacturing Systems.

[73]  S. Lee,et al.  Miscibility and crystallization behaviour of poly(l-lactide)/poly(p-vinylphenol) blends , 1998 .

[74]  M. Hillmyer,et al.  The influence of block copolymer microstructure on the toughness of compatibilized polylactide/polyethylene blends , 2004 .

[75]  Thomas Bley,et al.  Additive Biotech-Chances, challenges, and recent applications of additive manufacturing technologies in biotechnology. , 2017, New biotechnology.

[76]  Mehrshad Mehrpouya,et al.  The benefits of additive manufacturing for sustainable design and production , 2021 .

[77]  ChoiJin,et al.  4D Printing Technology: A Review , 2015 .

[78]  P. Dubois,et al.  Effect of expanded graphite/layered-silicate clay on thermal, mechanical and fire retardant properties of poly(lactic acid) , 2010 .

[79]  U. Meekum,et al.  PLA and two components silicon rubber blends aiming for frozen foods packaging applications , 2018 .

[80]  Chunhua Lu,et al.  Synthesis and Study of Shape-Memory Polymers Selectively Induced by Near-Infrared Lights via In Situ Copolymerization , 2017, Polymers.

[81]  S. Ray,et al.  Influence of nanoparticles and their selective localization on the structure and properties of polylactide-based blend nanocomposites , 2021 .

[82]  Martin L. Dunn,et al.  Advances in 4D Printing: Materials and Applications , 2018, Advanced Functional Materials.

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

[84]  Jack G. Zhou,et al.  Investigating the shape memory properties of 4D printed polylactic acid (PLA) and the concept of 4D printing onto nylon fabrics for the creation of smart textiles , 2017 .

[85]  M. Barletta,et al.  Investigation on shape recovery of 3D printed honeycomb sandwich structure , 2020 .

[86]  E. Fortunati,et al.  Microstructure and nonisothermal cold crystallization of PLA composites based on silver nanoparticles and nanocrystalline cellulose , 2012 .

[87]  U. Lafont,et al.  Additive manufacturing — A review of 4D printing and future applications , 2018, Additive Manufacturing.

[88]  Chul B. Park,et al.  Poly(lactic acid) crystallization , 2012 .

[89]  Xiaofan Luo,et al.  A functionally graded shape memory polymer , 2011 .

[90]  Robert Langer,et al.  Physical and mechanical properties of PLA, and their functions in widespread applications - A comprehensive review. , 2016, Advanced drug delivery reviews.

[91]  Seeram Ramakrishna,et al.  Additive Manufacturing of Biomaterials − The Evolution of Rapid Prototyping , 2019, Advanced Engineering Materials.

[92]  A. Savini,et al.  A short history of 3D printing, a technological revolution just started , 2015, 2015 ICOHTEC/IEEE International History of High-Technologies and their Socio-Cultural Contexts Conference (HISTELCON).

[93]  M. Saeb,et al.  Inclusion of modified lignocellulose and nano-hydroxyapatite in development of new bio-based adjuvant flame retardant for poly(lactic acid) , 2018, Thermochimica Acta.

[94]  H. Qi,et al.  Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding , 2015 .

[95]  Shunichi Hayashi,et al.  Structure and properties of shape-memory polyurethane block copolymers , 1996 .

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

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

[98]  R. Matsuzaki,et al.  A review of 3D and 4D printing of natural fibre biocomposites , 2020, Materials & Design.

[99]  F. Memarian,et al.  Thermo‐mechanical and shape memory behavior of TPU/ABS/MWCNTs nanocomposites compatibilized with ABS‐g‐MAH , 2019 .

[100]  Hui He,et al.  Favorable Thermoresponsive Shape Memory Effects of 3D Printed Poly(Lactic Acid)/Poly(ε‐Caprolactone) Blends Fabricated by Fused Deposition Modeling , 2020 .

[101]  Rubens Maciel Filho,et al.  Poly-lactic acid synthesis for application in biomedical devices - a review. , 2012, Biotechnology advances.

[102]  Chen Wang,et al.  New directions in the chemistry of shape memory polymers , 2014 .

[103]  Yanju Liu,et al.  Origami-inspired self-deployment 4D printed honeycomb sandwich structure with large shape transformation , 2020, Smart Materials and Structures.

[104]  Xiaofan Luo,et al.  Preparation and Characterization of Shape Memory Elastomeric Composites , 2009 .

[105]  E. Saino,et al.  Multifunctional bionanocomposite films of poly(lactic acid), cellulose nanocrystals and silver nanoparticles , 2012 .

[106]  Jie Song,et al.  Thermal Responsive Shape Memory Polymers for Biomedical Applications , 2011 .

[107]  S. Lim,et al.  Toughening of polylactide by melt blending with linear low‐density polyethylene , 2003 .

[108]  C. Lewis,et al.  A review of shape memory polymers bearing reversible binding groups , 2016 .

[109]  Tao Xi Wang,et al.  A Brief Review of the Shape Memory Phenomena in Polymers and Their Typical Sensor Applications , 2019, Polymers.

[110]  Rahul Sahay,et al.  3D printing in tissue engineering: a state of the art review of technologies and biomaterials , 2020, Rapid Prototyping Journal.

[111]  Ventola Cl Medical Applications for 3D Printing: Current and Projected Uses. , 2014 .

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

[113]  T. Chou,et al.  Shape memory behavior and recovery force of 4D printed laminated Miura-origami structures subjected to compressive loading , 2018, Composites Part B: Engineering.

[114]  Annamaria Gisario,et al.  The Potential of Additive Manufacturing in the Smart Factory Industrial 4.0: A Review , 2019, Applied Sciences.

[115]  M. Saeb,et al.  Flame retardant polymer materials: An update and the future for 3D printing developments , 2021 .

[116]  C. J. Carriere,et al.  Interfacial tension of poly(lactic acid)/polystyrene blends , 2002 .

[117]  Patrick T. Mather,et al.  Review of progress in shape-memory polymers , 2007 .

[118]  M. Barletta,et al.  Additive manufacturing of polyhydroxyalkanoates (PHAs) biopolymers: Materials, printing techniques, and applications. , 2021, Materials science & engineering. C, Materials for biological applications.

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

[120]  Tsering Dolma,et al.  Analysis of Shape Memory Properties in 3D Printed PLA , 2018 .

[121]  Tuan Liu,et al.  Shape memory Poly(lactic acid) binary blends with unusual fluorescence , 2020 .

[122]  Amy M. Peterson,et al.  Effect of layer thickness on irreversible thermal expansion and interlayer strength in fused deposition modeling , 2017 .

[123]  Jun Fu,et al.  Instability/collapse of polymeric materials and their structures in stimulus-induced shape/surface morphology switching , 2014 .

[124]  Xiabin Jing,et al.  Polylactide-based polyurethane and its shape-memory behavior , 2006 .

[125]  T. Guraya,et al.  Semi-automated quantification of the microstructure of PLA/clay nanocomposites to improve the prediction of the elastic modulus , 2018 .

[126]  Simona Bronco,et al.  Thermal degradation of poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) and their blends upon melt processing , 2009 .

[127]  Yanju Liu,et al.  Direct-Write Fabrication of 4D Active Shape-Changing Structures Based on a Shape Memory Polymer and Its Nanocomposite. , 2017, ACS applied materials & interfaces.

[128]  Yanan Wang,et al.  An accurate finite element approach for programming 4D-printed self-morphing structures produced by fused deposition modeling , 2020 .

[129]  P. Makvandi,et al.  4 D-Printed Dynamic Materials in Biomedical Applications: Chemistry, Challenges, and Their Future Perspectives in the Clinical Sector. , 2020, Journal of medicinal chemistry.

[130]  J. M. Nóbrega,et al.  On the use of high viscosity polymers in the fused filament fabrication process , 2017 .

[131]  Jie Ren,et al.  Preparation and properties of biodegradable poly(lactic acid)/poly(butylene adipate-co-terephthalate) blend with glycidyl methacrylate as reactive processing agent , 2009 .

[132]  J. Oh Polylactide (PLA)-based amphiphilic block copolymers: synthesis, self-assembly, and biomedical applications , 2011 .

[133]  Mahdi Bodaghi,et al.  4D Printing Self-Morphing Structures , 2019, Materials.

[134]  Eujin Pei,et al.  Technological considerations for 4D printing: an overview , 2018 .

[135]  L. Mattoso,et al.  Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films , 2016, Journal of Polymers and the Environment.

[136]  Shen Su,et al.  Polylactide (PLA) and Its Blends with Poly(butylene succinate) (PBS): A Brief Review , 2019, Polymers.

[137]  S. Magdassi,et al.  4D Printed Hydrogels: Fabrication, Materials, and Applications , 2020, Advanced Materials Technologies.

[138]  I. Rousseau Challenges of Shape Memory Polymers : A Review of the Progress Toward Overcoming SMP's Limitations , 2008 .

[139]  M. Hillmyer,et al.  Polyethylene-poly(L-lactide) diblock copolymers: synthesis and compatibilization of poly(L-lactide)/polyethylene blends , 2001 .

[140]  A. Kashani,et al.  Additive manufacturing (3D printing): A review of materials, methods, applications and challenges , 2018, Composites Part B: Engineering.

[141]  Sunpreet Singh,et al.  3D printed biodegradable functional temperature-stimuli shape memory polymer for customized scaffoldings. , 2020, Journal of the mechanical behavior of biomedical materials.

[142]  L. Lamberti,et al.  3D printed biodegradable composites: An insight into mechanical properties of PLA/chitosan scaffold , 2020 .

[143]  Xuelian Wu,et al.  Mechanisms of the Shape Memory Effect in Polymeric Materials , 2013 .

[144]  Sanghun Shin,et al.  Effect of 3D printing raster angle on reversible thermo-responsive composites using PLA/paper bilayer , 2020, Smart Materials and Structures.

[145]  L. Lim,et al.  Processing technologies for poly(lactic acid) , 2008 .

[146]  Quan Zhang,et al.  Smart three-dimensional lightweight structure triggered from a thin composite sheet via 3D printing technique , 2016, Scientific Reports.

[147]  Feng Xu,et al.  4D Bioprinting for Biomedical Applications. , 2016, Trends in biotechnology.

[148]  Ji Zhao,et al.  Radial Compressive Property and the Proof-of-Concept Study for Realizing Self-expansion of 3D Printing Polylactic Acid Vascular Stents with Negative Poisson’s Ratio Structure , 2018, Materials.

[149]  A. Zolfagharian,et al.  Reversible energy absorbing meta-sandwiches by FDM 4D printing , 2020, International Journal of Mechanical Sciences.

[150]  Jinsong Leng,et al.  Personalized 4D printing of bioinspired tracheal scaffold concept based on magnetic stimulated shape memory composites , 2019, Composites Science and Technology.

[151]  M. Barletta,et al.  4D printing of shape memory polylactic acid (PLA) components: Investigating the role of the operational parameters in fused deposition modelling (FDM) , 2021 .

[152]  H. Kim,et al.  Electrospinning biomedical nanocomposite fibers of hydroxyapatite/poly(lactic acid) for bone regeneration. , 2006, Journal of biomedical materials research. Part A.

[153]  M. Saeb,et al.  Bio-epoxy resins with inherent flame retardancy , 2019, Progress in Organic Coatings.

[154]  K. Shakesheff,et al.  Chemical and Morphological Analysis of Surface Enrichment in a Biodegradable Polymer Blend by Phase-Detection Imaging Atomic Force Microscopy , 1998 .