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This paper aims to provide a review of four-dimensional (4D) printing using fused-deposition modeling (FDM). 4D printing is an emerging innovation in (three-dimensional) 3D printing that encompasses active materials in the printing process to create not only a 3D object but also a 3D object that can perform an active function. FDM is the most accessible form of 3D printing. By providing a review of 4D printing with FDM, this paper has the potential in educating the many FDM 3D printers in an additional capability with 4D printing.

This is a review paper. The approach was to search for and review peer-reviewed papers and works concerning 4D printing using FDM. With this discussion of the shape memory effect, shape memory polymers and FDM were also made.

4D printing has become a burgeoning area in addivitive manufacturing research with many papers being produced within the past 3-5 years. This is especially true for 4D printing using FDM. The key findings from this review show the materials and material composites used for 4D printing with FDM and the limitations with 4D printing with FDM.

Limitations to this paper are with the availability of papers for review. 4D printing is an emerging area of additive manufacturing research. While FDM is a predominant method of 3D printing, it is not a predominant method for 4D printing. This is because of the limitations of FDM, which can only print with thermoplastics. With the popularity of FDM and the emergence of 4D printing, however, this review paper will provide key resources for reference for users that may be interested in 4D printing and have access to a FDM printer.

Practically, FDM is the most popular method for 3D printing. Review of 4D printing using FDM will provide a necessary resource for FDM 3D printing users and researchers with a potential avenue for design, printing, training and actuation of active parts and mechanisms.

Continuing with the popularity of FDM among 3D printing methods, a review paper like this can provide an initial and simple step into 4D printing for researchers. From continued research, the potential to engage general audiences becomes more likely, especially a general audience that has FDM printers. An increase in 4D printing could potentially lead to more designs and applications of 4D printed devices in impactful fields, such as biomedical, aerospace and sustainable engineering. Overall, the change and inclusion of technology from 4D printing could have a potential social impact that encourages the design and manufacture of such devices and the treatment of said devices to the public.

There are other 4D printing review papers available, but this paper is the only one that focuses specifically on FDM. Other review papers provide brief commentary on the different processes of 4D printing including FDM. With the specialization of 4D printing using FDM, a more in-depth commentary results in this paper. This will provide many FDM 3D printing users with additional knowledge that can spur more creative research in 4D printing. Further, this paper can provide the impetus for the practical use of 4D printing in more general and educational settings.

The purpose of this paper is to study the influence of calcium sulfate whiskers (CSWs) on the thermodynamic properties and shape memory properties of epoxy/cyanate ester shape memory composites.

To improve the mechanical properties of shape memory cyanate ester (CE)/epoxy polymer (EP) resin, high performance CSWs were used to reinforce the thermo-induced shape memory CE/EP composites and the shape memory CSW/CE/EP composites were prepared by molding. The effect of CSW on the mechanical properties and shape memory behavior of shape memory CE/EP composites was investigated.

After CSW filled the shape memory CE/EP composites, the bending strength of the composites is greatly improved. When the content of CSW is 5 Wt.%, the bending strength of the composite is 107 MPa and the bending strength is increased by 29 per cent compared with bulk CE/EP resin. The glass transition temperature and storage modulus of the composites were improved in CE/EP resin curing system. However, when the content of CSW is more than 10 Wt.%, clusters are easily formed between whiskers and the voids between whiskers and matrix increase, which will lead to the decrease of mechanical properties of composites. The results of shape memory test show that the shape memory recovery time of the composites decreases with the decrease of CSW content at the same temperature. In addition, the shape recovery ratio of the composites decreased slightly with the increase of the number of thermo-induced shape memory cycles.

A simple way for fabricating thermo-activated SMP composites has been developed by using CSW.

The outcome of this study will help to fabricate the SMP composites with high mechanical properties and the shape memory CSW/CE/EP composites are expected to be used in space deployable structures.

A review on additive manufacturing (AM) of shape memory polymer composites (SMPCs) is put forward to highlight the progress made up to date, conduct a critical review and show the limitations and possible improvements in the different research areas within the different AM techniques. The purpose of this study is to identify academic and industrial opportunities.

This paper introduces the reader to three-dimensional (3 D) and four-dimensional printing of shape memory polymers (SMPs). Specifically, this review centres on manufacturing technologies based on material extrusion, photopolymerization, powder-based and lamination manufacturing processes. AM of SMPC was classified according to the nature of the filler material: particle dispersed, i.e. carbon, metallic and ceramic and long fibre reinforced materials, i.e. carbon fibres. This paper makes a distinction for multi-material printing with SMPs, as multi-functionality and exciting applications can be proposed through this method. Manufacturing strategies and technologies for SMPC are addressed in this review and opportunities in the research are highlighted.

This paper denotes the existing limitations in the current AM technologies and proposes several directions that will contribute to better use and improvements in the production of additive manufactured SMPC. With advances in AM technologies, gradient changes in material properties can open diverse applications of SMPC. Because of multi-material printing, co-manufacturing sensors to 3D printed smart structures can bring this technology a step closer to obtain full control of the shape memory effect and its characteristics. This paper discusses the novel developments in device and functional part design using SMPC, which should be aided with simple first stage design models followed by complex simulations for iterative and optimized design. A change in paradigm for designing complex structures is still to be made from engineers to exploit the full potential of additive manufactured SMPC structures.

Advances in AM have opened the gateway to the potential design and fabrication of functional parts with SMPs and their composites. There have been many publications and reviews conducted in this area; yet, many mainly focus on SMPs and reserve a small section to SMPC. This paper presents a comprehensive review directed solely on the AM of SMPC while highlighting the research opportunities.

This paper aims to exploit shape-memory polymers as self-healable materials. The underlying mechanism involved the thermal transitions as well as the enrichment of the healing reagents and the closure of the crack surfaces due to shape recovery. The multi-stimuli-triggered shape memory composite was capable of self-healing under not only direct thermal but also electrical stimulations.

The shape memory epoxy polymer composites comprising the AgNWs and poly (ε-caprolactone) were fabricated by dry transfer process. The morphologies of the composites were investigated by the optical microscope and scanning electron microscopy (SEM). The electrical conduction and the Joule heating effect were measured. Furthermore, the healing efficiency under the different stimuli was calculated, whose dependence on the compositions was also discussed.

The AgNWs network maintained most of the pathways for the electrons transportation after the dry transfer process, leading to a superior conduction and flexibility. Consequently, the composites could trigger the healing within several minutes, as applied with relatively low voltages. It was found that the composites having more the AgNWs content had better electrically triggered performance, while 50 per cent poly (ε-caprolactone) content endowed the materials with max healing efficiency under thermal or electrical stimuli.

The findings may greatly benefit the application of the intelligent polymers in the fields of the multifunctional flexible electronics.

Most studies have by far emphasized on the direct thermal triggered cases. Herein, a novel, flexible and conductive shape memory-based composite, which was capable of self-healing under the thermal or electrical stimulations, has been proposed.

This article aims to present a systematic and up-to-date account of carbon-based reinforcements, including carbon nanotube (CNT), carbon nanofibre (CNF), carbon black (CB), carbon fibre (CF) and grapheme, in shape-memory polymer (SMP) for electrical actuation.

Studies exploring carbon-based reinforcement in SMP composites for electrically conductive performance and Joule heating triggered shape recovery have been included, especially for the principle design, characterisation and shape recovery behaviour, making the article a comprehensive account of the systemic progress in SMP composite incorporating conductive carbon reinforcement.

SMPs are fascinating materials and have attracted great academic and industrial attention owing to their significant macroscopic shape deformation in the presence of an appropriate stimulus. The working mechanisms, the physico requirements and the theoretical origins of the different types of carbon-based reinforcement SMP composites have been discussed. Current research and development on the fabrication strategies of carbon-based reinforcement SMP composites have been summarised.

A systematic review is to evaluate carbon-based reinforcements in SMPs for electrical actuation and discuss recent developments and future applications.

Carbon-based reinforcements in SMPs can be used as smart deployable space structure in the broad field of aerospace technologies.

To reveal the research and development of utilising CNT, CNF, CB, CF and grapheme to achieve shape recovery of SMP composites through electrically resistive heating, which will significantly benefit the research and development of smart materials and systems.

The purpose of this paper is to provide a review of recent systematic and comprehensive advancement in electrospun polymer fiber and their composites with shape memory property.

The nanofiber manufacture technique is initially reviewed. Then, the influence of electrospinning parameters and actuation method has been discussed. Finally, the study concludes with a brief review of recent development in potential applications.

Shape memory polymer (SMP) nanofibers are a type of smart materials which can change shape under external stimuli (e.g. temperature, electricity, magnetism, solvent). In general, such SMP nanofibers could be easily fabricated by mature electrospinning technique. The nanofiber morphology is mainly affected by the electrospinning parameters, including applied voltage, tip-to-collector distance, viscosity of solution, humidity and molecular weight. For actuation method, most SMP nanofibers and their composites can change their shapes in response to heat, magnetic field or solvent, while few can be driven by electricity. Compared with the block SMPs, electrospun SMP nanofibers’ mat with porosity and low mechanical property have a wide potential application field including tissue engineering, drug delivery, filtration, catalysis.

This paper provides a detailed review of shape memory nanofibers: fabrication, actuation and potential application, in the near future.

Epoxy (EP) and polye-caprolactone (PCL) are typical dual-shape memory polymer (DSMP). To get excellent triple-shape memory effect (TSME) polymer composites which are made from EP and PCL. Miscible PCL/EP blend composites have been investigated and compared to the TSMEs with electrospun PCL microfiber membranes/EP composites. Clay montmorillonite (MMT)-modified electrospun PCL microfiber membranes were prepared to improve the shape memory fixities of electrospun PCL microfiber membranes/EP composites.

The morphologies of electrospun PCL microfiber membranes and the cross section of PCL/EP composites were studied using a field emission scanning electron microscope (FE-SEM), and the existence of MMT was confirmed by a transmission electron microscope. Thermal mechanical properties were observed by a differential scanning calorimeter (DSC) and a dynamic thermomechanical analysis machine, and the TSMEs were also determined through dynamic mechanical analysis.

Results indicate that the TSMEs of electrospun PCL microfiber membranes/EP composites were excellent, whereas the TSMEs of PCL/EP blend composites were poor. The TSMEs of PCL electrospun microfiber membranes/EP composites significantly improved with the addition of the PCL electrospun microfiber modified with moderate MMT.

Adding a moderate content of MMT into the electrospun PCL fibers, could improve the TSME of the PCL fiber membranes/EP composites. This study was to create a simple and effective method that can be applied to improve the performance of other SMP.

A novel triple-shape memory composite were made from dual-shape memory EP and electrospun PCL fiber membranes.

This paper aims to exploit shape memory polymer (SMP) composite as multifunctional coatings for protecting substrates from surface wear and bacterial. The efficiency of added nano or micro-sized particles in enhancing the properties of SMP was investigated. This study also attempts to use a low-cost and effective spraying approach to fabricate the coatings. The coatings are expected to have good conformability with the substrate and deliver multi-functional performance, such as wrinkle free, wear resistance, thermal stability and antimicrobial property.

High-performance SMP composite coatings or thin films were fabricated by a home-made continuous spray-deposition system. The morphologies of the coatings were studied using the scanning electron microscope and the transmission electron microscope. The abrasion properties were evaluated by Taber Abraser test, and thermo-gravimetric analysis was carried out to investigate the thermal properties of prepared composites. The antimicrobial property was determined by the inhibition zone method using E. coli. The thermally responsive shape memory effect of the resulting composites was also characterized.

The morphology analysis indicated that the nanoclay was distributed on the surface of the coating which resulted in a significant improvement of the wear property. The wear resistance of the coatings with nanoclay was improved as much as 40 per cent compared with that of the control sample. The thermo-gravimetric analysis revealed that the weight loss rate of composites with nanoclay was dropped over 40 per cent. The SMP coating with zinc oxide (ZnO) showed excellent antimicrobial effect. The shape recovery effect of SMP/nanoclay and SMP/ZnO composites can be triggered by external heating and the composites can reach a full shape recovery within 60 s.

This study proposed a continuous spray-deposition fabrication of SMP composite coatings, which provides a new avenue to prepare novel multi-functional coatings with low cost.

Most studies have emphasized on the sole property of SMP composites. Herein, a novel SMP composite coating which could deliver multi-functionality such as wrinkle free, wear resistance, thermal stability and antimicrobial property was proposed.

The purpose of this paper is to study the interfacial effect on mechanical properties of the cellulose nano crystal (CNC)–shape memory polymer (SMP) composites by using combination of the theoretical and experimental approaches.

SMP composites were fabricated by introducing CNCs into crystalline shape memory polyurethane. The morphological, thermal and mechanical properties were comprehensively investigated. Theoretical approach based upon the percolation model was used to simulate the storage modulus E’ variation of the composites in crystalline and amorphous states, respectively. The classic two-phase percolation model was used for the amorphous-state composites. Furthermore, a three-phase model consisting of interfacial regions was created for the crystalline-state composites.

The deviation of nano fillers mechanical reinforcements was disclosed as the composites triggered thermal transitions. Modified percolation theory involving the interfacial effects greatly enhanced the simulation accuracy.

The study made the traditional percolating theory suitable for dynamic modulus and polymorphs polymers in terms of mechanics, which may extend the potential application.

The findings may greatly benefit the development of novel interfacial reinforcing theory and intelligent polymeric nanocomposites featuring polymorphs and dynamic properties.

This paper aims to create and to study multifunctional shape memory polymer (SMP) composites having temperature-sensing and actuating capabilities by embedding thermochromic particles within the polymer matrix.

The multifunctional materials were fabricated following a process consisting of blending (of the thermochromic particles and the SMP at various ratios), mixing, degasing, moulding and thermal curing, prepared by incorporating thermochromic particles within the polymer. The effect of the thermochromic particles on the thermomechanical properties and thermally responsive shape memory effect of the resulting multifunction SMP composites were characterised and interpreted.

It was found that exposure of the composites to temperatures above 70°C led to a pronounced change of their colour that was recorded by the thermal and electrical actuation approaches and was reproducibly reversible. It was also found that the colour of the composites was independent of the mechanical state of the SMP. Such effects enabled monitoring of the onset of the set/release temperature of the SMP matrix. Furthermore, the combination of thermochromic additive and the SMP resulted in significantly improved thermomechanical strength, absorption of infrared radiation and the temperature distribution of the SMP composites.

The temperature-sensing and actuating capabilities of the polymeric shape memory composites developed through this study will help to extend the field of potential applications of such composites to fields including sensors, actuators, security labels and information dissemination, where colour indication is an advantageous feature.

The SMP composites capable of temperature sensing and actuating are novel.