Engineering the shape memory parameters of graphene/polymer nanocomposites through atomistic simulations: On the effect of nanofiller surface treatment

This paper aims to comprehend the mechanisms underlying the shape memory behavior of polylactic acid infused with graphene functionalized by four groups of -OH, -CH3, -NH2, and tethered polymer layer. Applying molecular dynamics simulation, it is revealed that the graphene surface treatment enhances the shape fixity ratio of nanocomposites monotonically by increasing the physical cross-linking points within the polymer matrix. The improvement would be even more pronounced by increasing the coverage degree of small functional groups and grafting density of the covalently bonded polymer chains. Monitoring the key parameters illustrates that contrary to the OH groups, which improve the shape recovery value, the other functional groups degrade it by prohibiting the polymer chains mobility. Attempts to explore the governing mechanism demonstrate that shape fixity is improved when the difference between the potential energy variations in the loading and unloading stages increases. Interestingly, shape recovery is only under the influence of conformational entropy, and it is not affected by the potential energy. As such, we also probe variations of the radius of gyration during the recovery stage to address the role of different functionalization procedures on the reported shape recovery parameter.

Shape Memory Materials from Rubbers

Smart materials are much discussed in the current research scenario. The shape memory effect is one of the most fascinating occurrences in smart materials, both in terms of the phenomenon and its applications. Many metal alloys and polymers exhibit the shape memory effect (SME). Shape memory properties of elastomers, such as rubbers, polyurethanes, and other elastomers, are discussed in depth in this paper. The theory, factors impacting, and key uses of SME elastomers are all covered in this article. SME has been observed in a variety of elastomers and composites. Shape fixity and recovery rate are normally analysed through thermomechanical cycle studies to understand the effectiveness of SMEs. Polymer properties such as chain length, and the inclusion of fillers, such as clays, nanoparticles, and second phase polymers, will have a direct influence on the shape memory effect. The article discusses these aspects in a simple and concise manner.

A variable stiffness morphing skin: preparation and properties

In the course of flight, morphing skins play an important role in morphing aircrafts. Shape memory polymer (SMP) with variable stiffness performance is a good candidate material for skin. In this paper, a series of SMP morphing skins were prepared from hydro-epoxy resin (HEP), carboxyl-terminated butadiene acrylonitrile (CTBN) and maleic anhydride (MA). By adjusting molecular weight and content of CTBN, in-plane properties and out-of-plane properties of morphing skins can be adjusted. Due to the in-plane tensile stress acting on the skin during flight, tensile test was carried out to study its in-plane performance. After testing, skin can resist maximum in-plane tensile strength of 63.7 MPa. As for the out-of-plane performance of the skin, shape memory test was studied in this paper. All morphing skins have 100% shape fixity rate (Rf) and fast shape recovery rate (Rr). When toughened by CTBN of 10% of 4000 molecular weight with a mass fraction, the skin can recover its out-of-plane deformed shape in 33s. The SMP skins were proved to be a promising candidate for morphing skins.

Effects of graphene nanoplatelets on bio-based shape memory polymers from benzoxazine/epoxy copolymers actuated by near-infrared light

Novel near-infrared (NIR) light-induced bio-based shape memory polymers (SMPs) were prepared from copolymers of vanillin/furfurylamine-based benzoxazine monomer (V-fa monomer) and epoxidized castor oil (ECO). Incorporation of graphene nanoplatelets (GNPs) as photothermal fillers into the copolymers provided shape memory properties under near-infrared (NIR) light actuation. The effects of GNP content on photothermal, thermal, dynamic mechanical, morphology, and shape memory properties of the bio-based benzoxazine/epoxy copolymers (V-fa/ECO copolymers) were investigated. The results showed that the addition of GNPs significantly improved the photothermal, thermal, and dynamic mechanical properties of the copolymers. The uniform dispersion of 3 wt% GNPs in the V-fa/ECO copolymers resulted in the highest shape memory performance with shape fixity of 92% and shape recovery of 99% upon NIR light actuation. The recovery time decreased with the increment of GNP content, and the V-fa/ECO copolymers filled with GNPs displayed good execution in the repeated fold-deploy, in which the shape fixity and shape recovery values were close to the original specimen. Therefore, the outstanding properties of V-fa/ECO copolymers filled with GNPs had a potential to be excellent SMPs under NIR actuation.

HEAT-TRIGGERED SHAPE MEMORY EFFECT OF PEROXIDE CROSS-LINKED ETHYLENE–METHACRYLIC ACID COPOLYMER/NITRILE–BUTADIENE RUBBER THERMOPLASTIC VULCANIZATES WITH SEA-ISLAND STRUCTURE

ABSTRACT Designing shape memory polymers (SMPs) based on thermoplastic vulcanizates (TPVs) is an essential research topic. An efficient SMP is designed with typical sea-island structured ethylene–methacrylic acid copolymer/nitrile–butadiene rubber (EMA/NBR) TPVs in which the heat-control switched phase performed by the EMA phase is related to the shape fixity ability. The results show that the heat-triggered SMPs exhibit surprising shape memory properties (shape fixity >95%, shape recovery >95%, and fast recovery speed <30 s at the switching temperature of 95 °C). Through X-ray diffraction characterization, it is seen that the shape fixity of TPVs is achieved mainly through ethylene crystallization. The switching temperature is largely determined by the melting temperature (98 °C) obtained by differential scanning calorimetery.

Thermo-Responsive Shape Memory Behavior of Methyl Vinyl Silicone Rubber/Olefin Block Copolymer Blends via Co-Crosslinking

Shape memory polymers (SMPs) are developed by blending and cross-linking polymers which include crystalline domains and cross-linked networks. In this paper, we describe the morphology, thermal and shape memory behavior of methyl vinyl silicone rubber (MVMQ)/olefin block copolymer (OBC) blends prepared by a melt-blending and chemical cross-linking method. MVMQ without crystalline domains could not hold its temporary shape. After introducing the OBC, the obtained blends exhibited excellent dual shape memory properties. The cross-linking networks of MVMQ acted as reversible domains, while crystalline regions of OBC worked as fixed domains. When the blending ratio of MVMQ/OBC was 50/ 50, the blend had both a high shape fixity ratio and shape recovery ratio.

PENGARUH VARIASI JUMLAH BAHAN PENGISI CARBON BLACK TERHADAP SIFAT MEKANIK DAN KARAKTERISTIK KARET ALAM PENGINGAT BENTUK

Indonesia memiliki potensi komoditi karet alam yang besar, dengan modifikasi kimia karet alam dapat di design menjadi material pintar seperti halnya polimer sintetik lainnya. Material pintar yang dikembangkan pada penelitian ini adalah material shape memory atau pengingat bentuk. Material pengingat bentuk yaitu material yang memiliki kemampuan mengingat bentuk permanen, diprogram untuk menjadi bentuk tertentu dibawah lingkungan tertentu (seperti suhu dan pH), dan mampu kembali ke bentuk awalnya. Material pengingat bentuk berpotensi untuk diaplikasikan menjadi sensor, aktuator, alat kesehatan maupun spare part alat transportasi. Karet alam pengingat bentuk dibuat dengan metode swelling cross linked vulkanisat karet alam di dalam larutan asam stearat dengan suhu 75⁰C - 80⁰C dalam waterbath selama 1 jam. Tujuan dari penelitian ini adalah untuk mempelajari pengaruh variasi jumlah bahan pengisi (carbon black filler) pada 5 sampel (C1, C2, C3, C4, C5) terhadap sifat mekanik dan parameter pengingat bentuk. Hasil pengujian kuat tarik menunjukkan vulkanisat blanko memiliki kecenderungan nilai kuat tarik yang lebih tinggi dibandingkan vulkanisat yang mengalami treatment dengan asam stearat. Nilai shape recovery vulkanisat karet alam pengingat bentuk berkisar 76,9- 95,8% dan nilai shape fixity sebesar 14,8-26,1%.

Block Copolymers of Poly(ω-Pentadecalactone) in Segmented Polyurethanes: Novel Biodegradable Shape Memory Polyurethanes

In this report, the synthesis of poly(ω-pentadecalactone) (PPDL) (co)polymers and their incorporation into polyurethanes (PUs) are reported. Optimal conditions for the ring-opening polymerization (ROP) of ω-pentadecalactone (PDL) using dibutyltin dilaurate catalyst were established. For the synthesis of linear and crosslinked PUs, 50 kDa poly(ε-caprolactone) (PCL) and 1,6-hexamethylenediisocyanate (HDI) were used. The obtained polyurethanes were characterized by Attenuated Total Reflectance Fourier-Transform Infrared spectroscopy (AT-FTIR), differential scanning calorimetry (DSC), and dynamical mechanical analysis (DMA). The DMA of the selected sample showed a rubbery plateau on the storage modulus versus temperature curve predicting shape memory behavior. Indeed, good shape memory performances were obtained with shape fixity (Rf) and shape recovery (Rr) ratios.

Development of Thermo-Responsive Polycaprolactone–Polydimethylsiloxane Shrinkable Nanofibre Mesh

A thermally activated shape memory polymer based on the mixture of polycaprolactone (PCL) and polydimethylsiloxane (PDMS) was fabricated into the nanofibre mesh using the electrospinning process. The added percentages of the PDMS segment in the PCL-based polymer influenced the mechanical properties. Polycaprolactone serves as a switching segment to adjust the melting temperature of the shape memory electro-spun PCL–PDMS scaffolds to our body temperature at around 37 °C. Three electro-spun PCL–PDMS copolymer nanofibre samples, including PCL6–PDMS4, PCL7–PDMS3 and PCL8–PDMS2, were characterised to study the thermal and mechanical properties along with the shape memory responses. The results from the experiment showed that the PCL switching segment ratio determines the crystallinity of the copolymer nanofibres, where a higher PCL ratio results in a higher degree of crystallinity. In contrast, the results showed that the mechanical properties of the copolymer samples decreased with the PCL composition ratio. After five thermomechanical cycles, the fabricated copolymer nanofibres exhibited excellent shape memory properties with 98% shape fixity and above 100% recovery ratio. Moreover, biological experiments were applied to evaluate the biocompatibility of the fabricated PCL–PDMS nanofibre mesh. Owing to the thermally activated shape memory performance, the electro-spun PCL–PDMS fibrous mesh has a high potential for biomedical applications such as medical shrinkable tubing and wire.

Effect of PEW and CS on the Thermal, Mechanical, and Shape Memory Properties of UHMWPE

Modified ultra-high-molecular-weight polyethylene (UHMWPE) with calcium stearate (CS) and polyethylene wax (PEW) is a feasible method to improve the fluidity of materials because of the tense entanglement network formed by the extremely long molecular chains of UHMWPE, and a modified UHMWPE sheet was fabricated by compression molding technology. A Fourier-transform infrared spectroscopy test found that a new chemical bond was generated at 1097 cm−1 in the materials. Besides, further tests on the thermal, thermomechanical, mechanical, and shape memory properties of the samples were also conducted, which indicates that all properties are affected by the dimension and distribution of crystal regions. Moreover, the experimental results indicate that the addition of PEW and CS can effectively improve the mechanical properties. Additionally, the best comprehensive performance of the samples was obtained at the PEW content of 5 wt % and the CS content of 1 wt %. In addition, the effect of temperature on the shape memory properties of the samples was investigated, and the results indicate that the shape fixity ratio (Rf) and the shape recovery ratio (Rr) can reach 100% at 115 °C and 79% at 100 °C, respectively, which can contribute to the development of UHMWPE-based shape memory polymers.