Acrylate-based Shape-memory Polymers Research Articles

4D Printing of Smart Polymer Nanocomposites: Integrating Graphene and Acrylate Based Shape Memory Polymers.

The ever-increasing demand for materials to have superior properties and satisfy functions in the field of soft robotics and beyond has resulted in the advent of the new field of four-dimensional (4D) printing. The ability of these materials to respond to various stimuli inspires novel applications and opens several research possibilities. In this work, we report on the 4D printing of one such Shape Memory Polymer (SMP) tBA-co-DEGDA (tert-Butyl Acrylate with diethylene glycol diacrylate). The novelty lies in establishing the relationship between the various characteristic properties (tensile stress, surface roughness, recovery time, strain fixity, and glass transition temperature) concerning the fact that the print parameters of the laser pulse frequency and print speed are governed in the micro-stereolithography (Micro SLA) method. It is found that the sample printed with a speed of 90 mm/s and 110 pulses/s possessed the best batch of properties, with shape fixity percentages of about 86.3% and recovery times as low as 6.95 s. The samples built using the optimal parameters are further subjected to the addition of graphene nanoparticles, which further enhances all the mechanical and surface properties. It has been observed that the addition of 0.3 wt.% of graphene nanoparticles provides the best results.

4D printing of shape memory polymer via liquid crystal display (LCD) stereolithographic 3D printing

In this study, we report a new epoxy acrylate based shape memory polymer (SMP) fabricated by Liquid crystal display (LCD) Stereolithographic 3D printing. The printed 3D object has a high resolution and high transparency in visible light region. The uniaxial tensile tests showed enhanced tensile toughness and tunable mechanical properties. The fix-recovery and cycle tests indicated high shape recovery properties including high shape recovery rate and excellent cycling stability. In addition, a smart electrical valve actuator was fabricated that can be used in fast heat or electricity responsive electrical circuits. LCD 3D printing provides a low-cost and high efficient way to fabricate fast responsive SMP, which can be used in wide applications in various fields on aerospace engineering, biomedical devices, soft robots and electronic devices.

Effect of the addition of diurethane dimethacrylate on the chemical and mechanical properties of tBA-PEGDMA acrylate based shape memory polymer network

There is a great demand for the synthesis of acrylate based thermoset shape memory polymer (SMP) associated with one monomer and one crosslinker such as tert-butyl acrylate (t-BA) with poly (ethylene glycol) dimethacrylate (PEGDMA). The present work describes the synthesis of a new thermoset SMP wherein a second monomer such as diurethane dimethacrylate (DUDMA) has been added to the existing tBA + PEGDMA SMP matrix. The synthesized thermoset shape memory polymer exhibited a glass transition temperature (Tg) of 55 °C, higher Young's Modulus of 3.23 GPa, transmittance of 95% and 100% shape recovery. The SMP exhibited response to both thermal and chemical stimuli. The shape recovery rate of the SMP network is 20 s compared to 24 s observed for SMP based on tBA + PEGDMA. The obtained SMP is very transparent and possesses higher stiffness (8 MPa) and hence may be suitable for biomedical shape memory lens and orthopedic application.

Four-dimensional printing of a novel acrylate-based shape memory polymer using digital light processing

Shape memory polymers (SMPs), a type of promising smart materials, are gradually applied into digital light processing (DLP) technology to realize four-dimensional (4D) printing. However, there is still a great lack of shape memory photosensitive resins suitable for DLP. In this work, novel acrylate-based photosensitive resins designed for DLP are prepared to fabricate SMP parts with tert-Butyl acrylate/1, 6-hexanediol diacrylate (tBA/HDDA) networks. The influence of crosslinker concentration on the shape memory and mechanical properties is systematically investigated. The results show that the developed SMP with 10 wt% crosslinker can withstand 16 consecutive cycles and retain extremely high shape recovery ratio of 100% even after 14 cycles, the one with 20 wt% crosslinker possesses the best shape fixity ratio of over 96%, and the storage modulus can reach up to 1.48 × 103 MPa with 50 wt% crosslinker. Furthermore, these 4D printed SMPs only spends 7–13 s in the 180° shape recovery, indicating a good shape recovery rate. This work confirms that the designed SMPs have potential applications in many areas due to their excellent shape memory performance, and provides valuable guidance for the shape memory properties optimization of other SMPs.

Enhanced mechanical properties of acrylate based shape memory polymer using grafted hydroxyapatite

In the present study, the effect of grafted and ungrafted hydroxyapatite (HAp) filler on the mechanical properties of acrylate based shape memory polymer (SMP) composite is reported. HAp is grafted with polyethylene glycol methacrylate (PEGMA) monomer to avoid agglomeration and the same is embedded as reinforcement in tBA – PEGDMA matrix (70 wt% tBA: tert-butyl acrylate +30 wt% PEGDMA: polyethylene glycol dimethacrylate). The grafting process improved the interfacial interactions of the particles, dispersed in the polymer system and subsequently enhanced the mechanical properties of the shape memory polymer composites. The morphology of HAp particles is investigated by field emission scanning electron microscopy. The mechanical properties of SMP composites are evaluated at room temperature and above glass transition temperature (Tg) with grafted and ungrafted HAp particles. The addition of grafted HAp significantly improved the tensile strength (40%) and shape recovery rate (25%) of the SMP composite when compared to the SMP composite containing ungrafted HAp. SMP composite containing grafted HAp exhibited higher cell viability compared to the neat SMP and the SMP composite containing ungrafted HAp.

Tailored poly(ethylene) glycol dimethacrylate based shape memory polymer for orthopedic applications

Shape-memory polymers (SMPs) are stimuli-responsive materials known for their outstanding ability to be actuated from temporary shape into original shape. Because of this unique functionality SMPs are promising materials for diverse technological applications including smart biomedical devices. In this article, the work has been focused towards tailoring the SMP precursor and crosslinker wt% to obtain biocompatible acrylate based shape memory polymer with glass transition temperature (Tg) close to human body temperature. Methacrylate based shape memory polymer networks are synthesized via free radical polymerization by varying the wt% of t-butyl acrylate (tBA) and poly(ethylene glycol) dimethacrylate (PEGDMA) as crosslinker. The Tg is found to increase from 28 to 45°C with increasing tBA amount. The SMP synthesized from 70wt% of tBA and 30wt% of PEGDMA possess Tg close to human body temperature and is tested for cytotoxicity with two different cell lineages, osteosarcoma (MG-63) cells, and human keratinocyte (HaCaT) cells. The synthesized SMP is found to be non-cytotoxic. Thus the investigated biocompatible shape memory polymer network can be a promising soft substrate for passive thermomechanical stimulation which can adapt and meet specific needs of in vitro or in vivo orthopedic Superior Labrum Anterior and Posterior (SLAP) medical devices.

Effect of crosslinking and long-term storage on the shape-memory behavior of (meth)acrylate-based shape-memory polymers

This work highlights the free- and fixed-strain shape-memory response of amorphous (meth)acrylate-based shape-memory polymers as the level of crosslinking is varied from uncrosslinked to highly crosslinked (corresponding to a decrease in failure strains and overall increase in rubbery moduli and failure stresses). The effect of long-term storage on the free-strain shape-memory response is also considered. Tensile deformation levels during the shape-memory cycle are 90% of failure strain values to determine the full extent of free- and fixed-strain recovery behavior. All materials demonstrate full shape-recovery under free-strain conditions (material is unconstrained during recovery); however, total recoverable strains increase with decreasing crosslinking level, with uncrosslinked and lightly crosslinked materials recovering strains on the order of 3–10× that of moderately and highly crosslinked materials. In contrast, under fixed-strain conditions (material is fully constrained in the fixed shape during recovery), the magnitude of recovery stress generation increases with increasing crosslinking level, with highly crosslinked materials demonstrating recovery stress levels 4–20× that of lightly crosslinked and uncrosslinked materials. The ability to produce recovery stresses on par with those reached during deformation also increases with crosslinking level. Stored-shape fixation and free-strain recovery levels remain stable after long-term storage in the deformed temporary state at 20 °C; however, recovery onset temperatures increase (by up to 9 °C) with storage time spanning ∼1 year, as do rates of free-strain recovery (by up to 9×), due to physical aging. Results indicate that aging could potentially be used as a method for shape-memory response optimization.

Shape memory polymer foams from emulsion templating

Shape memory polymers (SMPs) change their shape under a stimulus (thermal, chemical, light) and return from an imposed temporary shape to their permanent, original shape. SMPs usually contain “permanent” domains that determine the permanent shape (chemical or physical crosslinks) and “reversible” domains that determine the temporary shape, usually by heating above a glass transition temperature or a melting point (Tm). Compared to fully dense SMPs, SMP foams can undergo higher temporary deformations and can exhibit higher deformations when they recover. In this paper, SMP foams based upon (meth)acrylates with crystallizable long side-chains were synthesized through emulsion-templating within nanoparticle-stabilized high internal phase Pickering emulsions where the nanoparticles also served as crosslinking centers. The nature of the polymer backbone affected the nature of the crystalline phase for identical side chains. The SMP foams at room temperature maintained the temporary shape (a strain of 0.7) imposed above the Tm and exhibited good recovery upon reheating for all four compression–recovery cycles. While the methacrylate-based SMP exhibited a single-stage recovery, the acrylate-based SMP, with identical side-chains, exhibited a two-stage recovery that can be associated with the existence of two crystalline phases. The recovery behavior was described using Kelvin–Voigt units in series with the dependence of viscosity on temperature described using a WLF-like relationship.