Thermal-responsive Shape Memory Polymers Research Articles

Development of Multiwalled Carbon Nanotubes/Halloysite Nanotubes Reinforced Thermal Responsive Shape Memory Polymer Nanocomposites for Enhanced Mechanical and Shape Recovery Characteristics in 4D Printing Applications.

The mechanical and shape-recovery characteristics of 4D-printed thermally responsive shape-memory polyurethane (SMPU) reinforced with two types of reinforcements, multiwalled carbon nanotubes (MWCNTs) and Halloysite nanotubes (HNTs), are investigated in the present study. Three weight percentages of reinforcements (0, 0.5, and 1) in the SMPU matrix are considered, and the required composite specimens are obtained with 3D printing. Further, for the first time, the present study investigates the flexural test for multiple cycles to understand the 4D-printed specimens' flexural behavior variation after shape recovery. The 1 wt% HNTS-reinforced specimen yielded higher tensile, flexural, and impact strengths. On the other hand, 1 wt% MWCNT-reinforced specimens exhibited quick shape recovery. Overall, enhanced mechanical properties were observed with HNT reinforcements, and a faster shape recovery was observed with MWCNT reinforcements. Further, the results are promising for the use of 4D-printed shape-memory polymer nanocomposites for repeated cycles even after a large bending deformation.

Mechanical and Shape Recovery Characterization of MWCNTs/HNTs-Reinforced Thermal-Responsive Shape-Memory Polymer Nanocomposites.

Mechanical and shape recovery characteristics of thermal-responsive shape-memory polyurethane (SMPU) reinforced with two types of reinforcements, multiwalled carbon nanotubes (MWCNTs) and halloysite nanotubes (HNTs), were studied in the present research work. Three weight percentages of reinforcement (0, 0.5 and 1%) in the SMPU matrix were considered, and the required composite specimens were obtained through injection moulding. Tensile, flexural, impact and shape recovery behaviours were studied experimentally. Further, flexural tests were performed for multiple cycles to understand the specimens' flexural strength variation after shape recovery. The concentration of both reinforcements (MWCNTs and HNTs) considered in the present study significantly improved mechanical properties and shape recovery.

Evaluation on the Seal Performance of SMP-Based Packers in Oil Wells

Packers based on shape memory polymers (SMPs) are an emerging technology that have the advantages of compact structure, easy manufacture, and adaptability to complex wells. This paper proposes a finite element model to simulate the setting process and mechanical response of an SMP packer. The investigated material is an epoxy-based thermal responsive SMP, whose relaxation modulus and thermal expansion coefficient were measured at different temperatures. Based on the experimental data, the model describes the viscoelastic behavior of the SMP using the generalized Maxwell model. The results show that the SMP packer could provide sufficient contact stress under downhole conditions, even after the stress was relaxed. A further parametric study revealed that the most significant factor in sealing effects is the wellbore pressure, followed by the interference between the packer and the annular, the seal length, the pre-compression, and the setting temperature. High downhole pressures require more significant contact stress and increase the risk of slip between the packer and casing wall by promoting shear stress. Increasing the seal length and interference enhances the contact stress and mitigates the shear stress to improve the seal performance. Pre-compression and setting temperatures are minor factors that have little influence on sealability.

In Situ Reversible Tuning from Pinned to Roll-Down Superhydrophobic States on a Thermal-Responsive Shape Memory Polymer by a Silver Nanowire Film.

Shape memory polymer (SMP) surfaces with tunable wettability have attracted extensive attention due to their widespread applications. However, there have been rare reports on in situ tuning wettability with SMP materials. In this paper, we reported a kind of distinct superhydrophobic SMP microconed surface on the silver nanowire (AgNW) film to achieve in situ reversible transition between pinned and roll-down states. The mechanism is taking advantage of the in situ heating functionality of the silver nanowire film by voltage, which provides the transition energy for SMP to achieve the fixation and recovery of temporary shape. It is noteworthy that the reversible transition could be repeated many times (>100 cycles), and we quantitatively investigate the shape memory ability of microcones with varied height and space under different applied voltages. These results show that the tilted microcones could recover its original upright state under a small voltage (4-11 V) in a short time, and the shortest recovery time is about 0.5 min under an applied voltage of ∼10 V. Finally, we utilize SMP microcone arrays with tunable wettability to realize lossless droplet transportation, and the tilted microconed surface also achieves liquid unidirectional transport due to its anisotropic water adhesion force. The robust microconed SMP surface with reversible morphology transitions will have far-ranging applications including droplet manipulation, reprogrammable fog harvesting, and so on.

Superhydrophobicity-memory surfaces prepared by a femtosecond laser

Superhydrophobicity-memory surface that can transform its surface morphology and wettability in response to heat was successfully prepared by using femtosecond laser to directly induce hierarchical micropillar array on the surface of a thermal-responsive shape-memory polymer (SMP). When the resultant surface was pressed by an external load to make the micropillars lean to one side, the superhydrophobicity would weaken caused by the deformation of the micro/nanoscale structures. Interestingly, the original surface morphology and wettability could recover just through a simple heating process due to the excellent macro/microscopic shape-memory effect of such polymer. Even after 10 cycles of pressing-heating treatments, the surface was also able to re-obtain its original ultralow-adhesive superhydrophobicity. In addition to the restorable property, the superhydrophobicity of the as-prepared surface was very stable since the laser-induced microstructure on the SMP could withstand various harsh treatments/environments, such as sandpaper abrasion, tape peeling, UV irradiation, and the immersion in different pH solutions. The superhydrophobicity-memory surface was successfully used as a rewritable platform for directional liquid transportation. It is anticipated that the laser-induced hierarchical micropillars with superhydrophobicity-memory property will have significant applications in tunable wettability, liquid/droplet manipulation, and chemical engineering.

4D printing – fused deposition modeling printing with thermal-responsive shape memory polymers

Shape memory polymers (SMPs), as stimuli-responsive shape-changing polymers, change their deformed shape to pre-determined one under external stimuli, such as temperature, chemicals, light, etc. This research as part of the project in which employs four-dimensional (4D) printing technology to develop smart textile and wearable products. It describes the 4D printing process of the SMPs and their carbon nanotube composites. More specifically, the process begins with the SMPs pellet treatment for making the filament as input material for fused deposition modeling (FDM) type three-dimensional (3D) printer, then printing and finally testing the printed objects. The printed objects effectively perform the characteristics of SMPs in experiments as presented. Based on the achieved results, this process could be easily adapted to other research that related to 4D printing using SMPs. More research is needed to implement the 4D printing technology for the project and low-cost and mass production further.

Enabling the sunlight driven response of thermally induced shape memory polymers by rewritable CH3NH3PbI3 perovskite coating

(CH3NH3)PbI3 perovskite coating not only makes normal widely used thermal responsive shape memory polymers (SMPs) responsive to direct sunlight due to the strong photo-thermal effect of the coating, but also allows the material to be able to flexibly switch between photo-sensitive and photo-inert states by erasing and re-applying the coating.

In vivo tissue responses to thermal-responsive shape memory polymer nanocomposites

To explore the safe use of thermal-responsive shape memory polymers (SMPs) as minimally invasive tissue scaffolds, we recently developed a class of biodegradable POSS-SMP nanocomposites exhibiting stable temporary shape fixing and facile shape recovery within a narrow window of physiological temperatures. The materials were covalently crosslinked from star-branched building blocks consisting a bioinert polyhedral oligomeric silsesquioxane (POSS) core and 8 degradable poly( d, l-lactide) (PLA) arms. Here we examine the degradation profiles and immunogenicity of POSS-SMPs as a function of the PLA arm lengths using a rat subcutaneous implantation model. We show that POSS-SMPs elicited a mild foreign body type immune response upon implantation. The degradation rates of POSS-SMPs, both in vitro and in vivo, inversely correlated with the length of the PLA chains within the crosslinked amorphous network. Upon in vivo degradation of POSS-SMPs, a second acute inflammatory response was elicited locally, and the inflammation was able to resolve over time without medical interventions. One year after the implantation of POSS-SMPs, no pathologic abnormities were detected from the vital/scavenger organs examined. These minimally immunogenic and biodegradable SMPs are promising candidates for scaffold-assisted tissue repair where both facile surgical delivery and controlled degradation of the scaffold are desired for achieving optimal short-term and long-term clinical outcomes.

High performance shape memory polymer networks based on rigid nanoparticle cores

Smart materials that can respond to external stimuli are of widespread interest in biomedical science. Thermal-responsive shape memory polymers, a class of intelligent materials that can be fixed at a temporary shape below their transition temperature (T(trans)) and thermally triggered to resume their original shapes on demand, hold great potential as minimally invasive self-fitting tissue scaffolds or implants. The intrinsic mechanism for shape memory behavior of polymers is the freezing and activation of the long-range motion of polymer chain segments below and above T(trans), respectively. Both T(trans) and the extent of polymer chain participation in effective elastic deformation and recovery are determined by the network composition and structure, which are also defining factors for their mechanical properties, degradability, and bioactivities. Such complexity has made it extremely challenging to achieve the ideal combination of a T(trans) slightly above physiological temperature, rapid and complete recovery, and suitable mechanical and biological properties for clinical applications. Here we report a shape memory polymer network constructed from a polyhedral oligomeric silsesquioxane nanoparticle core functionalized with eight polyester arms. The cross-linked networks comprising this macromer possessed a gigapascal-storage modulus at body temperature and a T(trans) between 42 and 48 degrees C. The materials could stably hold their temporary shapes for > 1 year at room temperature and achieve full shape recovery <or= 51 degrees C in a matter of seconds. Their versatile structures allowed for tunable biodegradability and biofunctionalizability. These materials have tremendous promise for tissue engineering applications.

Review of electro-active shape-memory polymer composite

Shape-memory polymers (SMPs) have been one of the most popular subjects under intensive investigation in recent years, due to their many novel properties and great potential. These so-called SMPs by far surpass shape-memory alloys and shape-memory ceramics in many properties, e.g., easy manufacture, programming, high shape recovery ratio and low cost, and so on. However, they have not fully reached their technological potential, largely due to that the actuation of shape recovery in thermal-responsive SMPs is normally only driven by external heat. Thus, electro-activate SMP has been figured out and its significance is increasing in years to come. This review focuses on the progress of electro-activate SMP composites. Special emphases are given on the filler types that affect the conductive properties of these composites. Then, the mechanisms of electric conduction are addressed.