3D polymeric scaffolds towards biomedical applications

4D printing: Pragmatic progression in biofabrication

Four-dimensional (4D) printing is used to describe three-dimensional (3D)-printed objects with properties that change over time. Shape memory polymers (SMPs) are representative materials for 4D printing technologies. The ability to print geometrically complex, free-standing forms with SMPs is crucial for successful 4D printing. In this study, an SMP capable of frontal polymerization featuring exothermic self-propagation was synthesized by adding cyclooctene to a poly(dicyclopentadiene) network, resulting in switching segments. The rheological properties of this SMP were controlled by adjusting incubation time. A nozzle system was designed such that the SMP could be printed with simultaneous polymerization to yield a free-standing structure. The printing speed was set to 3 cm min−1 according to the frontal polymerization speed. A free-standing, hexagonal spiral was successfully printed and printed spiral structure showed excellent shape memory performance with a fixity ratio of about 98% and a recovery ratio of 100%, thereby demonstrating the 3D printability and shape memory performance of frontally polymerizable SMPs.

Personalized 4D printing of bioinspired tracheal scaffold concept based on magnetic stimulated shape memory composites

Shape memory polymer (SMP) systems exhibiting semicrystalline- elastomer blends, such as thermoplastic polyurethane and polylactic acid have been well studied, but their use in biomedical shape memory applications has been limited by their high activation temperature. SMPs are capable of deformation and recovery through the activation of an external stimuli, such as temperature. Critical criteria for SMPs used in biomedical applications is achieving a stimulus temperature close to 37°C while still experiencing sufficient shape recovery. A polymer’s glass transition temperature has been well defined as the SMP system’s activation temperature and therefore should be decreased to achieve a decreased activation temperature. In this work, a well-known, biocompatible plasticizer, polyethylene oxide (PEO), was added to thermoplastic polyurethane (TPU) – polylactic acid (PLA) SMP blends to observe the plasticizing effect on the structural, thermal, mechanical, and shape memory properties of the polymer blends. Additionally, the geometry of the fabricated SMP samples was tailored to further enhance the shape memory effect through a bowtie honeycomb structure. Our results suggest that the addition of PEO into the SMP system may be an effective method for decreasing the polymer’s glass transition temperature through the alteration of the polymer chain structure. With the addition of 30% PEO, the glass transition temperature of the TPU/PLA blend was successfully decreased from 62.4°C to 34.6°C while achieving 86.5% shape recovery when activated at 37°C, which is only a 5% decrease in shape recovery when activated at 50°C. These results suggest that the addition of a biocompatible plasticizer may overcome the limitation of employing temperature activated SMP systems in biomedical applications, and enhances the potential of these materials for reconfigurable structures, energy dissipation systems, and SHM in civil engineering applications.

Four-dimensional (4D) printing is regarded as a methodology that links 3D printing to time, which is characterized by the evolution of predetermined structures or functions for the printed object after applying stimulation. This dynamic feature endows 4D printing the potential to be intelligent, attracting wide attention from academia and industry. The transformation of shape and function is both obtained from the programming of the object endowed by the intrinsic characteristics of the material or by the manufacturing technology. Therefore, it is necessary to understand 4D printing from the perspective of both mechanism and manufacturing. Here, the state-of-the-art 4D printing polymer was summarized, beginning with the classifications, and leading to the mechanisms, stimulations, and technologies. The links and differences between 4D printing polymer and shape memory polymer, between 4D printing and 3D printing were highlighted. Finally, the biomedical applications were outlined and the perspectives were discussed.

Hybrid hinge structure with elastic hinge on self-folding of 4D printing using a fused deposition modeling 3D printer

4D printed and multi-stimulus responsive shape memory polymer nanocomposites developed on hydrogen bonding–metal-phenolic sacrificial network: Application for hazardous chemical operations soft robots

Herein, direct 4D printing of thermoresponsive shape memory polymers (SMPs) by the fused deposition modeling (FDM) method that enables programing of 2D objects during printing for autonomous 2D‐to‐3D shape transformations via simply heating is focused on. The programming process during printing is investigated through designs and experiments. The capability of programming SMPs during printing is illustrated by prestrain and bending capabilities, which are highly related to printing settings, such as nozzle temperature, print speed, layer height, infill patterns, and ratio of active parts in a bilayer structure. A nearly linear relationship for prestrain and bending parameters is experimentally revealed for different printing factors. Quantitative results are presented to be used as a guidance for designing complex 3D structures via 4D printing of 2D structures. Helix structure, twisting structure, DNA‐like structures, and functional gripper are designed to demonstrate the potential of direct FDM 4D printing for creating complex 3D structures from simple 2D structures with advantages over traditional manufacturing methods. It is shown that, by removing the need for a layer‐by‐layer stacking process to achieve a complex 3D shape, FDM can promote sustainability via 4D printing of autonomous 2D‐to‐3D shape transformer structures with lower materials, time, energy, and longer service life.

4 - 4D-printed low-voltage electroactive polymers modeling and fabrication

In the traditional 4D printing method using Shape Memory Polymer (SMP), the design process and preparation of 4d printing are complex. In this research, we proposed a design method of a temperature-driven SMP smart structure and made Realization. This smart structure also a bilayer structure use an SMP material in one printing process to realize the deformation in 4D printing. The design of the smart structure is mainly realized by parameter allocation in the printing process, such as print line width, print line height, print temperature, simulation temperature, and fill the form in Fused Deposition Modelling (FDM). Through experimental determination and analysis of statics and thermodynamics, our method fitting out the model relationship between process parameters and the curvature and strain of smart structure. This bilayer smart structure widely applied to the self-folding. In the example stage, this paper mainly uses PLA as an SMP material for the preparation of structure. Observing that the motion behaviors of the smart structure conformed to the model measured in this paper, the average accuracy of the strategy reaches 95%.

The complex nature of spinal cord injuries has provided much inspiration for the design of novel biomaterials and scaffolds which are capable of stimulating neural tissue repair strategies. Recently, conductive polymers have gained much attention for improving the nerve regeneration. In our previous study, a three-dimensional (3D) structure with reliable performance was achieved for electrospun scaffolds. The main purpose in the current study is formation of electrical excitable 3D scaffolds by appending polyaniline (PANI) to biocompatible polymers. In this paper, an attempt was made to develop conductive nanofibrous scaffolds, which can simultaneously present both electrical and topographical cues to cells. By using a proper 3D structure, two kinds of conductive scaffolds are compared with a non-conductive scaffold. The 3D nanofibrous core-sheath scaffolds, which are conductive, were prepared with nanorough sheath and aligned core. Two different sheath polymers, including poly(lactic-co-glycolic acid) PLGA and PLGA/PANI, with identical PCL/PANI cores were fabricated. Nanofibers of PCL and PLGA blends with PANI have fiber diameters of 234±60.8 nm and 770±166.6 nm, and conductivity of 3.17×10-5 S/cm and 4.29×10-5 S/cm, respectively. The cell proliferation evaluation of nerve cells on these two conductive scaffolds and previous non-conductive scaffolds (PLGA) indicate that the first conductive scaffold (PCL/ PANI-PLGA) could be more effective for nerve tissue regeneration. Locomotor scores of grafted animals by developed scaffolds showed significant performance of non-conductive 3D scaffolds. Moreover, the animal studies indicated the ability of two new types of conductive scaffolds as spinal cord regeneration candidates.

Despite great progress in four-dimensional (4D) printing, i.e. three-dimensional (3D) printing of active (stimuli-responsive) materials, the relatively low actuation force of the 4D printed structures often impedes their engineering applications. In this study, we use multimaterial inkjet 3D printing technology to fabricate shape memory structures, including a morphing wing flap and a deployable structure, which consist of active and flexible hinges joining rigid (non-active) parts. The active hinges, printed from a shape memory polymer (SMP), lock the structure into a second temporary shape during a thermomechanical programming process, while the flexible hinges, printed from an elastomer, effectively increase the actuation force and the load-bearing capacity of the printed structure as reflected in the recovery ratio. A broad range of mechanical properties such as modulus and failure strain can be achieved for both active and flexible hinges by varying the composition of the two base materials, i.e. the SMP and the elastomer, to accommodate large deformation induced during programming step, and enhance the recovery in the actuating step. To find the important design parameters, including local deformation, shape fixity and recovery ratio, we conduct high fidelity finite element simulations, which are able to accurately predict the nonlinear deformation of the printed structures. In addition, a coupled thermal-electrical finite element analysis was performed to model the heat transfer within the active hinges during the localized Joule heating process. The model predictions showed good agreement with the measured temperature data and were used to find the major parameters affecting temperature distribution including the applied voltage and the convection rate.

Although several force application concepts are known that can be used to deform shape memory polymers (SMPs) within the scope of programming, controlled deformation is challenging in the case of samples with a cylinder-like shape, which need to be homogeneously compressed starting from the lateral surface. To solve this problem, this contribution follows a material approach that takes advantage of four-dimensional (4D) printing. Fused filament fabrication (FFF) was used as an additive manufacturing (AM) technique to produce a thermoresponsive tool in a cylindrical shape from a polyether urethane (PEU) having a glass transition temperature (Tg) close to 55 °C, as determined by differential scanning calorimetry (DSC). Once it was 4D-printed, a sample of laser cut polyester urethane urea (PEUU) foam with a cylindrical wall was placed inside of it. Subsequent heating to 75 °C and keeping that temperature constant for 15 min resulted in the compression of the foam, because the internal stresses of the PEU were transferred to the PEUU, whose soft segments were completely molten at 65 °C as verified by DSC. Upon cooling to -15 °C and thus below the offset temperature of the soft segment crystallization transition of the PEUU, the foam was fixed in its new shape. After 900 days of storage at temperatures close to 23 °C, the foam recovered its original shape upon reheating to 75 °C. In another experiment, a 4D-printed cylinder was put into hibernation for 900 days before its thermoresponsiveness was investigated. In the future, 4D-printed tools may be produced in many geometries, which fit well to the shapes of the SMPs to be programmed. Beyond programming SMP foams, transferring the forces released by 4D-printed tools to other programmable materials can further expand technical possibilities.

Shape memory polymers (SMPs) are evolving intensively in smart materials research. SMPs can undergo large deformations, hold a temporary shape and then recover their original shape upon exposure to a particular external stimulus. The emerging development of fibre reinforced shape memory polymer composites (SMPCs) has improved SMPs’ mechanical properties to be comparable to modern fibre reinforced composites. Moreover, the inclusion of nanoparticles has enhanced the diversity in activation mechanisms and improved structural properties and durability.
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\nToday, the SMPCs are generally viewed as promising substances for engineered applications that have raised intensive interest among the scientists and engineers. Interestingly, stimulation by light enables unique and advanced shape memory effects (SMEs) in SMPCs that can fulfill the sophisticated demands of engineering. The ability to vary the light wavelength, intensity, periodicity, polarization and the irradiated position on the SMP component enables wavelength selective, reversible, sequential and multiple SMEs. Furthermore, light travel long distances in a vacuum, can be focussed onto a certain area, is safe to humans and, can be a control signal carrier and most notably, can be sent through optical fibres to extremely inaccessible areas.
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\nIncorporation of metallic, carbon and organic based photothermal fillers into a SMP matrix is a convenient proven method to prepare light activated shape memory polymer composites (LASMPCs). These photothermal fillers convert electromagnetic radiation into thermal energy that triggers the SMP matrix. The current study comprehensively reviewed the performances, mechanisms, challenges and limitations of the existing LASMPC systems and associated optical technologies. Predominantly this research was intended to develop reinforced LASMPC systems and allied optical technologies applicable for large scale structural engineering applications.
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\nIn this study, styrene and bisphenol A epoxy based thermosets and polylactic acid (PLA) based thermoplastic SMPs were used as polymer matrix materials. Carbon fibre, glass fibre, multiwalled carbon nanotube (MWCNT) and rare earth organic complexes of Nd(TTA)3Phen and Yb(TTA)3Phen were used as reinforcement and photothermal fillers. The samples were produced by means of vacuum bagging, mould casting and 4D printing. Morphological investigations were conducted to identify the microstructure and manufacturability of the LASMPCs. The samples’ mechanical and physical properties were tested by standard test methods for polymer matrix composites. Dynamic mechanical analysis was carried out to determine the thermomechanical characteristics. The photothermal effect was investigated through thermal imaging and associated shape memory behaviours were studied through shape fixing and recovery experiments. A finite element analysis was performed with ABAQUS to simulate the photothermal heating behaviour.
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\nThe current study established a material development framework for LASMPC materials and presented apt manufacturing methods for structural and large scale engineering applications. Different modes of light diffusion such as scattered low intensity light, focussed laser beams and light delivery through fibre optics were proved for structural LASMPCs. Sequential and selective wavelength activation of structural LASMPCs are presented. The FEA simulation provided additional understanding on light exposed LASMPCs’ 3-dimensional heating behaviour. Embedding a D-shaped optical fibre in an LASMPC created a single unit smart actuator, which was remotely activated by light. It was proven that flexible radiation shields can reduce the unanticipated shape recovery of LASMPCs components and protect the LASMPCs from polymer degradation due to radiation.
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\nThe improvements to their structural properties and innovative remote activation methodologies have justified LASMPCs’ aptness for space engineering applications. This study has proven its successful completion by three selected case studies of space applications. An LASMPC solar panel array model was sequentially deployed in four recovery steps. In a vacuum, a space habitat structure model was compressed to a third of its volume and then recovered its original shape. A 4D printed boom structure model was tested, proving customized LASMPC structures for sophisticated space equipment fabrication. The deployable LASMPC structures can reduce the occupied room in spacecraft. The improvements to the structural properties of LASMPCs while keeping the SME, understanding on thermomechanical and photothermal behaviours, remote actuation through optical fibres, radiation shields and the insight to space applications are the most significant novel outcomes of this study. This thesis opens up windows of opportunity for the scientific and engineering communities to provide innovative solutions to realize the sophisticated large scale engineering demands in aerospace and space applications and beyond.

The rapid development and advancements in field of shape memory alloys (SMAA) has tremendously increased the progress in four-dimensional (4D) printing. The conventional 4D printing will require skilled manpower but utilization of reversibility aspect achieved using self adjusting external stimuli will eliminate the necessity of sophisticated devices and human intervention in 4D printing. The components created using reversible 4D printing can be reused after each recovery cycle that suits the current industry requirements. This review is divided into three sections: The first section starts with a detailed illustration of different mechanisms associated with SMAA and shape memory polymers SMPP along with an illustration of realistic 3D-printed SMAA and SMPP. The second section of this paper deals with the different methods of manufacture with the advantages and disadvantages of different types of SMAA. The third section deals with the mechanisms associated with SMPP, namely (1) Thermo-responsive mechanism, (2) Chemo-responsive mechanism, and (3) Photo-responsive mechanism along with a detailed insight into the aspect of repeatability and reversibility. The fourth section presents an exhaustive review of the application of SMAA and SMPP in civil engineering. The last section of this work throws light on the challenges faced in 4D reversible printing of SMAA and SMPP along with the potential solutions and presents directions for future research.