The term 4D printing refers to the idea that the shape or properties of a printed object can be changed when an external stimulus is applied. In this contribution, a temperature-responsive polymer Poly (N-vinyl caprolactam) (PNVCL), which is normally prepared via radical free polymerization, was used to justify the 4D printing concept. As a result, by using a Stereolithography (SLA) 3D printer, 4D prints were successfully prepared. These prints were able to demonstrate intelligent and reversible expansion/shrinkage behaviour as the temperature increases and decreases. Additionally, in order to examine the differences in chemical structure, thermal properties, mechanical properties, and swelling behaviours of the photopolymerised and printed parts, a series of characterisation tests, including Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), goniometry, tensile test, gel fraction measurement and pulsatile swelling study were performed on this study. In conclusion, the differences between polymerisation methods are significant; despite their chemical structures and thermal properties being similar, there were significant differences with regard to tensile properties, swellability and wettability of samples. The implications of conducting this study are remarkable, not only in providing a new way of preparing NVCL, but also in demonstrating the possibility of using 4D printed NVCL for practical applications.

The phase transitions of poly (N-vinyl caprolactam) (PNVCL) hydrogels are currently under investigation as possible materials for biomedical applications thanks to their thermosensitive properties. This study aims to use the photopolymerisation process to simulate the 4D printing process. NVCL-based polymers with different thermal properties and swellability were prepared to explore the possibility of synthetic hydrogels being used for 4D printing. In this contribution, the thermal behaviours of novel photopolymerised NVCL-based hydrogels were analysed. The lower critical solution temperature (LCST) of the physically crosslinked gels was detected using differential scanning calorimetry (DSC), ultraviolet (UV) spectroscopy, and cloud point measurement. The chemical structure of the xerogels was characterised by means of Fourier transform infrared spectroscopy (FTIR). Pulsatile swelling studies indicated that the hydrogels had thermo-reversible properties. As a result, the effect of varying the macromolecular monomer concentration was apparent. The phase transition temperature is increased when different concentrations of hydrophilic monomers are incorporated. The transition temperature of the hydrogels may allow for excellent flexibility in tailoring transition for specific applications, while the swelling and deswelling behaviour of the gels is strongly temperature- and monomer feed ratio-dependent.

Stimuli-responsive hydrogels have recently gained interest within shapeshifting applications due to their capabilities to expand in water and their altering swelling properties when triggered by stimuli, such as pH and heat. While conventional hydrogels lose their mechanical strength during swelling, most shapeshifting applications require materials to have mechanical strength within a satisfactory range to perform specified tasks. Thus, stronger hydrogels are needed for shapeshifting applications. Poly (N-isopropylacrylamide) (PNIPAm) and poly (N-vinyl caprolactam) (PNVCL) are the most popular thermosensitive hydrogels studied. Their close-to-physiological lower critical solution temperature (LCST) makes them superior candidates in biomedicine. In this study, copolymers made of NVCL and NIPAm and chemically crosslinked using poly (ethylene glycol) dimethacrylate (PEGDMA) were fabricated. Successful polymerisation was proven via Fourier transform infrared spectroscopy (FTIR). The effects of incorporating comonomer and crosslinker on the LCST were found minimal using cloud-point measurements, ultraviolet (UV) spectroscopy, and differential scanning calorimetry (DSC). Formulations that completed three cycles of thermo-reversing pulsatile swelling are demonstrated. Lastly, rheological analysis validated the mechanical strength of PNVCL, which was improved due to the incorporation of NIPAm and PEGDMA. This study showcases potential smart thermosensitive NVCL-based copolymers that can be applied in the biomedical shapeshifting area.

Four-dimensional printing is primarily based on the concept of 3D printing technology. However, it requires additional stimulus and stimulus-responsive materials. Poly-N-vinylcaprolactam is a temperature-sensitive polymer. Unique characteristics of poly-N-vinylcaprolactam -based hydrogels offer the possibility of employing them in 4D printing. The main aim of this study is to alter the phase transition temperature of poly-N-vinylcaprolactam hydrogels. This research focuses primarily on incorporating two additional monomers with poly-N-vinylcaprolactam: Vinylacetate and N-vinylpyrrolidone. This work contributes to this growing area of research by altering (increasing and decreasing) the lower critical solution temperature of N-vinylcaprolactam through photopolymerisation. Poly-N-vinylcaprolactam exhibits a lower critical solution temperature close to the physiological temperature range of 34–37 °C. The copolymers were analysed using various characterisation techniques, such as FTIR, DSC, and UV-spectrometry. The main findings show that the inclusion of N-vinylpyrrolidone into poly-N-vinylcaprolactam increased the lower critical solution temperature above the physiological temperature. By incorporating vinylacetate, the lower critical solution temperature dropped to 21 °C, allowing for potential self-assembly of 4D-printed objects at room temperature. In this case, altering the lower critical solution temperature of the material can potentially permit the transformation of the 4D-printed object at a particular temperature.

Poly (N-vinylcaprolactam) is a polymer that is biocompatible, water-soluble, thermally sensitive, non-toxic, and nonionic. In this study, the preparation of hydrogels based on Poly (N-vinylcaprolactam) with diethylene glycol diacrylate is presented. The N-Vinylcaprolactam-based hydrogels are synthesised by using a photopolymerisation technique using diethylene glycol diacrylate as a crosslinking agent, and Diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide as a photoinitiator. The structure of the polymers is investigated via Attenuated Total Reflectance–Fourier Transform Infrared Spectroscopy. The polymers are further characterised using differential scanning calorimetry and swelling analysis. This study is conducted to determine the characteristics of P (N-vinylcaprolactam) with diethylene glycol diacrylate, including the addition of Vinylacetate or N-Vinylpyrrolidone, and to examine the effects on the phase transition. Although various methods of free-radical polymerisation have synthesised the homopolymer, this is the first study to report the synthesis of Poly (N-vinylcaprolactam) with diethylene glycol diacrylate by using free-radical photopolymerisation, using Diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide to initiate the reaction. FTIR analysis shows that the NVCL-based copolymers are successfully polymerised through UV photopolymerisation. DSC analysis indicates that increasing the concentration of crosslinker results in a decrease in the glass transition temperature. Swelling analysis displays that the lower the concentration of crosslinker present in the hydrogel, the quicker the hydrogels reach their maximum swelling ratio.