Memory Properties Research Articles

Ultra-high stretchability and shape fixation rate shape memory polyurethanes based on cyclic polytetrahydrofuran molecular rings

Chemical cross-linking is commonly used to prevent slippage between molecular chains in shape memory polymers (SMPs) to improve shape return. However, chemical cross-linking makes SMPs less stretchable, and the disordered network structure reduces the ability of SMPs to maintain temporary shapes. To obtain ultra-high stretchability and better shape memory properties, a cyclic polymer (C-PTHF-OH) was introduced into the shape memory polyurethane (PUCX) network, and the PUCX network topology was controlled by adjusting the content of C-PTHF-OH molecular rings. PUC0.5 exhibited the highest shape fixation (99.9 %) and shape recovery (98.4 %), and the higher the content of the C-PTHF-OH molecular ring, the higher the elongation at break of the prepared PUCX, with a slight decrease in tensile strength. Compared to PUC0 (2000 % elongation at break and 32 MPa tensile strength) prepared from the linear polymer, PUC0.5 showed up to 2150 % elongation at break and 31 MPa tensile strength. This study provides new ideas for the design of network structures for SMPs and is a new paradigm introduced into the SMPs network by cyclic topological polymers.

Programming-via-spinning: Electrospun shape memory polymer fibers with simultaneous fabrication and programming

Porous shape memory polymer (SMP) scaffolds are promising ‘smart’ materials for potential use in a wide range of biomedical applications. Electrospinning provides an approach to produce fibrous SMP scaffolds to enhance their porosity, mass transfer, and flexibility. Here, we studied the effects of electrospinning parameters (rotating collector rotational speed and solvent) on shape memory and mechanical properties of a biostable thermoplastic polyurethane (PUr) SMP. Scanning electron microscopy confirmed that fiber diameter and tortuosity could be tuned using varied collector rotation speeds and/or solvents. Mechanical properties, including modulus, tensile strength, and ultimate elongation, were tuned independently of chemistry based on variations in fiber architectures. All scaffolds demonstrated shape memory properties. Additionally, due to strains that are trapped in the fibers during the electrospinning process, SMP fibers are programmed into a strained, temporary shape during the fabrication step. These fibers can be immediately triggered to recover to a non-strained primary shape after fabrication to reduce sample preparation time and complexity. As a proof-of-concept, bacterial protease-responsive SMPs were electrospun and exposed to S. aureus in programmed secondary shapes. Upon exposure to bacteria, these SMPs underwent shape recovery, which resulted in reduced bacterial attachment and biofilm formation. These materials could be employed as bacteria-responsive wound dressings in future work. Overall, electrospinning provides a valuable tool for tuning mechanical and shape memory properties independently from chemistry and for programming SMPs during fabrication to enable scale-up of electrospun SMP scaffolds.

4D printing of Nd-Fe-B composites with both shape memory and permanent magnet excitation deformation

Novel composite filaments are developed by mixing PLA, TPU, and Nd-Fe-B components and utilizing melt extrusion for 4D printing. The results reveal that the Nd-Fe-B magnetic particles are uniformly dispersed in the PLA/TPU polymer matrix, and the composite filaments meet the requirements of high-precision printing. Increasing the proportion of Nd-Fe-B magnetic particles in the composite contributes to higher remanence, coercivity, and magnetic energy product for the printed magnets. Under the 70 °C thermal stimulus, it has a high shape fixed ratio (>99 %), a high shape recovery ratio (>90 %), and a rapid response time (≤6.55 s). The magnetic particles accelerate the shape recovery process. Moreover, the petal-like structure and the hollow ball structure are designed and printed. After deformation, each structure can nearly fully recover its initial shape. This recovery is achieved through a non-contact stimulus response based on ’thermal-magnetic’ coupling. The grippers printed by the developed composite show comprehensive properties of shape memory and magnetically controlled smart gripping.

Achieving dual-phase structured Cu-Al-Mn-Si alloy with prominent shape memory properties via laser powder bed fusion

In this study, Cu-11.1Al-8.15Mn-0.37Si shape memory alloy was manufactured via laser powder bed fusion (LPBF) and compared with furnace-cooling cast samples. The LPBF-manufactured samples exhibited a dual-phase structure of L21 austenite and 2H martensite, along with uniformly distributed nanoscale Mn5Si3 precipitations observed via TEM. The 2H martensite presented a layer-like morphology and was confirmed to be induced by residual stress during the LPBF process. Such a dual-phase structure could be stabilized by Mn5Si3 precipitations, and yielded the concurrent presence of prominent superelastic (SE) and shape memory effect (SME) properties. Under 6 % pre-strain, LPBF-manufactured samples showed an 80 % SE rate and 83 % SME rate. The recovery SE and SME strain could be up to 4.2 % and 2.1 %. Compared to the cast sample, fracture compressive and tensile strain increased by 68.4 % and 33.3 %. This enhancement was due to regularly arranged columnar crystals and strong [001]//Z texture confirmed by EBSD. These findings suggest that LPBF has the potential to produce Cu-Al-Mn-Si alloys with prominent shape memory properties and provide references for an austenite-martensite dual-phase structure.

The polytannic acid‐Fe(III) functionalized graphene oxide in poly (propylene carbonate) nanocomposite enabling enhanced shape memory, UV‐resistance, and self‐healing performance

AbstractPolypropylene carbonate (PPC) is a promising candidate of substrate materials used for human wearable devices due to its excellent ductility and biocompatibility. However, PPC is prone to be deformed, thus resulting in poor shape recovery property. One effective solution is to construct composites. In this work, poly (tannic acid) with Fe3+ (FPTA) @ graphene oxide (GO) was added to fabricate FPTA@GO/PPC composites. The results show that FPTA@GO can construct a tight network of hydrogen bonds into PPC to improve shape memory and self‐healing properties. By varying the FPTA@GO content, the composites exhibit tunable shape memory property. Dynamic mechanical analysis confirms that FPTA@GO/PPC composites show better shape memory properties compared with pure PPC. 5 wt% FPTA@GO/PPC composite demonstrates superior shape fixation ratio (Rf = 99%) as well as superior shape recovery ratio (Rr = 94%) in 37°C. Moreover, 5 wt% FPTA@GO/PPC composite possesses great self‐healing efficiency of 81% and tensile strength (17.2 MPa). The UV absorption capacity of 5 wt% FPTA@GO/PPC is increased by 150% (far and mid‐UV regions) and 400% (near‐UV region) compared with pure PPC. Thus, FPTA@GO/PPC composites have potential applications in developing shape memory, self‐healing, and UV‐resistant materials for human wearable devices.

NIR responsive scaffold with multistep shape memory and photothermal-chemodynamic properties for complex tissue defects repair and antibacterial therapy

Complex tissue damage accompanying with bacterial infection challenges healthcare systems globally. Conventional tissue engineering scaffolds normally generate secondary implantation trauma, mismatched regeneration and infection risks. Herein, we developed an easily implanted scaffold with multistep shape memory and photothermal-chemodynamic properties to exactly match repair requirements of each part from the tissue defect by adjusting its morphology as needed meanwhile inhibiting bacterial infection on demand. Specifically, a thermal-induced shape memory scaffold was prepared using hydroxyethyl methacrylate and polyethylene glycol diacrylate, which was further combined with the photothermal agent iron tannate (FeTA) to produce NIR light-induced shape memory property. By varying ingredients ratios in each segment, this scaffold could perform a stepwise recovery under different NIR periods. This process facilitated implantation after shape fixing to avoid trauma caused by conventional methods and gradually filled irregular defects under NIR to perform suitable tissue regeneration. Moreover, FeTA also catalyzed Fenton reaction at bacterial infections with abundant H2O2, which produced excess ROS for chemodynamic antibacterial therapy. As expected, bacteriostatic rate was further enhanced by additional photothermal therapy under NIR. The in vitro and vivo results showed that our scaffold was able to perform high efficacy in both antibiosis, inflammation reduction and wound healing acceleration, indicating a promising candidate for the regeneration of complex tissue damage with bacterial infection.

Shape memory and mechanical properties of ESO modified epoxy/polyurethane semi-interpenetrating polymer networks for smart plaster

While numerous studies have explored the potential of shape memory materials in medical applications, the current research output is not enough for significant productivity in industrial products. In this research, a type of shape memory orthopedic plaster was fabricated by using epoxy/polyurethane interpenetrating networks modified with epoxidized soybean oil (ESO) and then compared with some commercial plasters. Polymer networks that were produced could be tailored to have glass transition temperatures (Tgs) within the range of 70–90 °C by changing the percentage composition of polyurethane and soybean oil. Shape recovery and fixity ratios in all samples were above 95 and 97 %. DMA results showed that IPNs with variable amount of soybean oil had lower glass transition temperature (Tg) and cross-link densities compared to IPNs without soybean oil. Based on the tensile test results, most samples exhibited an elastic modulus in the range of 280–400MPa, a level deemed somewhat acceptable when compared to commercial samples. Light microscope images had shown that the increase of polyurethane led to the phase separation of polymers, which was improved by the addition of soybean oil.

An approach on the estimation and temporal interaction of runoff: the band similarity method

ABSTRACT This study is based on the investigation of the performance of the band similarity (BS) method, which is quite new in the literature, in the prediction of flow and in determining the memory properties of the flow phenomenon. For this purpose, flow prediction models for the monthly flow data of the Sarız station, located in the Seyhan Basin in Türkiye, were produced first with the particle swarm optimization (PSO) algorithm. Second, these models were used in the BS method to create the BSPSO approach. Then, flow prediction was made for the same data set with support vector regression (SVR). In the test period, the standalone PSO, BSPSO, and SVR models achieved the most successful Nash–Sutcliffe efficiency (NSE) values of 0.516, 0.691, and 0.659, respectively. As a result, it was seen that BS increased the success of PSO by approximately 35%.

Reconfigurable dielectric engineered WSe2/HZO mem-transistor

Abstract Hybrid systems coupling 2D semiconductors with functional ferroelectrics are attracting increasing attention due to their excellent electronic/optoelectronic properties and new functionalities through the multiple heterointerface interaction. In our device architecture, interfacial states are introduced on the ferroelectric Hf0.5Zr0.5O2 thin film as gate dielectric layer for charge trapping effect. Utilizing the collaborative effects of charge trapping and ferroelectric polarization behavior, a multifunctional 2D WSe2/HZO memtransistor is demonstrated with ultra-low off-state (dark) current of 10-13 A, high on/off ratio of 106 and linear conductance update. This device exhibits reliable memory properties and tunable synaptic functions including short-term plasticity (STP)/ long-term plasticity (LTP), paired pulse facilitation (PPF), spike-timing dependent plasticity (STDP), synaptic potentiation/depression, and filtering in a single device. Extensive endurance tests ensure robust stability (1000 switching cycles, 2000 s holding time) and the synaptic weight update in the device exhibits excellent linearity. Based on the experimental data, our devices eventually achieve an accuracy of 94.8% in artificial neural network simulations. These results highlight a new approach for constructing hybrid systems coupling 2D semiconductors with functional ferroelectrics in a single device for tuning synaptic weight, optimizing circuit design, and building artificial neuromorphic computing systems.

Design of Triphenylamine-based D-π-A Systems for Efficient Ternary WORM Memory Devices.

The impact of various substituent moieties on the molecular framework of a conjugated D-A system in resistive switching memory property has been scrutinized through an array of novel D-π-A molecules. The synthesized molecules with triphenylamine (TPA) as the electron donor and dicyanovinylindanone (IC) as the electron acceptor demonstrated substantial non-volatile WORM (Write-Once Read-Many) memory behaviour with appreciable ON/OFF current ratios up to 105 and a lowest recorded threshold voltage of -0.80 V. The well-balanced combination of these potent electron donating and accepting units culminated in exceptional intramolecular charge transfer interactions and minimal band gap values (1.82-2.31 eV) for the molecules, as demonstrated by photophysical and electrochemical investigations. These factors, coupled with the thin-film morphological studies, corroborated the superior performance of the fabricated devices. A longer retention time of 2000s and an endurance of 100 cycles mark the substantial stability of the memory devices. Moreover, conversion from binary to ternary WORM memory was achieved by the effective tuning of the electronic properties of the D-A systems by various substituent moieties. Molecular simulation studies revealed that the resistive switching phenomenon arises from a synergistic interplay of charge transfer and charge trapping processes within these D-A systems.

Ultratough Supramolecular Polyurethane Featuring an Interwoven Network with Recyclability, Ideal Self-Healing and Editable Shape Memory Properties.

Developing multifunctional polymers with excellent mechanical properties, outstanding shape memory characteristics, and good self-healing properties is a formidable challenge. Inspired by the woven cross-linking strategy, a series of supramolecular polyurethane (PU) with an interwoven network structure composed of covalent and supramolecular cross-linking nodes have been successfully synthesized by introducing the ureido-pyrimidinone (UPy) motifs into the PU skeleton. The best-performing sample exhibited ultrahigh strength (∼77.2 MPa) and toughness (∼312.7 MJ m-3), along with an ideal self-healing efficiency (up to 90.8% for 6 h) and satisfactory temperature-responsive shape memory effect (shape recovery rates up to 96.9%). Furthermore, it ensured recyclability. These favorable properties are mainly ascribed to the effective dissipation of strain energy due to the disassembly and reconfiguration of supramolecular nodes (i.e., quadruple hydrogen bonds (H-bonds) between UPy units), as well as the covalent cross-linking nodes that maintain the integrity of the polymer network structure. Thus, our work provides a universal strategy that breaks through the traditional contradictions and paves the way for the commercialization of high-performance multifunctional PU elastomers.

Aqua jet integrated fiber laser machining of quaternary NiTiCuZr alloy

ABSTRACT Low thermal diffusivity of NiTi-based smart alloy results in concentrated heat accumulation during laser beam machining which rises to adverse thermal effects like heat-affected zones, residual stresses, and alterations in microstructure of shape memory alloy (SMA) system. The addition of Cu and Zr can reduce the thermal hysteresis in the phase transformation of NiTi SMAs. Minimizing thermal hysteresis is desirable in SMA applications where precise control of the phase transformation temperatures is required, such as in actuators, sensors, and medical devices. Therefore, aqua jet integrated laser (AJ-FLBM) machining is a suitable choice for smart materials that need to be machined with high precision and low heat affected zone. In this current research, the NiTiCuZr SMA is machined using AJ-FLBM to investigate the effects of process variables on surface characteristics measured using RSM-BBD approach. The surface quality was enhanced by 68.93% with a gradual decrease in laser power (P), cutting speed (CS), and an increase in frequency (F). Aqua jet integrated FLBM technique may reduce heat affected zone due to the removal of heat in areas near the cutting location. This was confirmed by the DSC test which reveals that optimal machining inputs do not alter shape memory properties.

Effect of annealing temperature on microstructure and memory properties of Fe-Mn-Si-Cr-Ni alloy prepared by additive manufacturing

Effect of annealing temperature on microstructure and memory properties of Fe-Mn-Si-Cr-Ni alloy prepared by additive manufacturing

4D printed Electroactive carbon fiber and carbon nanotube synergistically reinforced composites for supporting personalized insole

Smart footwear plays a vital role in walk correction, with mechanical behavior and shape memory effect (SME) being essential aspects. To create personalized smart insoles, we developed a novel blend of polylactic acid (PLA), thermoplastic polyurethane (TPU), and carbon nanotubes (CNT) via melting-extrusion for a continuous-fiber 3D printer. Diverse insole support unit-cell structures (triangular, rhombus, grid) were fabricated with PLA/TPU/CNT filaments, incorporating continuous carbon fibers (CFs) in the front, middle, and back parts of a particular orthopedic insole. The compressive strength and modulus of samples unexpectedly decreased upon CNT incorporation. However, CNT in the TPU phase improved the shape memory performance, shortening the recovery time by 58 %. CF-reinforced composites exhibited excellent mechanical properties and SME; the front triangular structure showed a 13.4 times increase in compressive strength and a 22.6 times increase in modulus compared to free-fiber composites. The printed samples demonstrated remarkable electro-induced shape memory properties due to the dual conductive network formed by CF and CNT. Our PLA/TPU/CNT/CF (nano-) composite is well-suited for personalized shape-memory insole applications, offering enhanced mechanical performance and electro-induced shape-memory capabilities.

Synergistic effects of cellulose nanocrystal on the mechanical and shape memory properties of TPU composites

Cellulose nanocrystal is a nanomaterial that has a large specific surface area, high surface energy, and high strength. As well, it is biocompatible, environmentally friendly, nontoxic, and can be extracted from biomass resources. Because of these features, cellulose nanocrystals can be used to improve the mechanical properties of polymer matrices with a shape memory effect and as a shape memory switch. In this study, a polytrimethylene ether glycol-based thermoplastic polyurethane (TPU)/cellulose nanocrystal (CNC) composite was prepared via an in-situ polymerization process to create a self-healing polymer matrix. Also, the effect of CNC doses in low concentrations (≤2 wt%) on the different properties of the resulting bio-nanocomposite was investigated. The results showed that the introduction of CNCs affects the hydrogen bonding within the polymer matrix and provides better thermal stability in the high temperature range than pure TPU. Furthermore, the samples with 0 wt%, 0.75 wt%, 1 wt%, and 2 wt% of CNC exhibited an increasing trend in tensile strength with values of 11.71 MPa, 18.95 MPa, 17.88 MPa, and 26.18 MPa, respectively, which indicates a remarkable improvement in mechanical strength. The shape memory behavior was also notably prominent in this polymer composite, where the composite containing 2 wt% of CNC showed the fastest recovery time (240 s) at 75 °C with the highest shape retention. Moreover, their flow behavior and deformation capacity were examined through rheology tests. Besides, docking simulations were conducted in silico to assess the interaction of the TPU/CNC composite with the DNA gyrase enzyme. The interaction between CNC/TPU composite and DNA gyrase was meticulously analyzed across 10 distinct conformations, yielding docking scores ranging from −6.5 Kcal/mol to −5.3 Kcal/mol. Overall, the physico-mechanical properties of the TPU/CNC composites were substantially enhanced with the incorporation of nanofillers.

Lignin-based vitrimer containing dynamic borate ester bonds with intrinsic photoconversion and excellent photothermal remoldability

The development of photoresponsive shape memory materials based on the photothermal conversion properties of lignin and the low activation energy of the dynamic covalent borate bond is of great importance. In this paper, a kind of lignin-based vitrimer polymer (LBP) containing dynamic boronic ester bonds was prepared by a “sulfhydryl-epoxy” click reaction and etherification reaction. The results show that the rigid segment EP-EL (lignin-based epoxy resin) and BDB (2,2′-(1,4-phenylene)-bis-[4-mercapto-1,3,2-dioxaneborane]) with benzene ring structure can impart tensile strength (20.8 MPa) to the LBP, while the flexible segment PEG imparts good elongation at break (15 %). The dynamic binding and dissociation exchange mechanism of the boronic ester bonds enables LBP to exhibit thermal remodelling properties (up to 36.2 %) and water-assisted self-healing properties at room temperature (up to 49.0 %). In addition, LBP exhibits excellent thermal and light-responsive shape memory properties due to its own photothermal conversion performance (photothermal conversion efficiency up to 18.2 %) and the dynamic boronic ester bond thermal activation bond exchange mechanism. The insulating properties of LBP make it suitable for use in high temperature protection circuit devices and light-responsive circuit devices. This study provides new insights into the design and application of Vitrimer and photoresponsive shape memory polymers, and also offers a new avenue for high-value utilization of lignin.

An Antiferromagnetic Neuromorphic Memory Based on Perpendicularly Magnetized CoO.

Antiferromagnets (AFMs) are ideal materials to boost neuromorphic computing toward the ultrahigh speed and ultracompact integration regime. However, developing a suitable AFM neuromorphic memory remains an aspirational but challenging goal. In this work, we construct such a memory based on the CoO/Pt heterostructure, in which the collinear insulating AFM CoO shows a strong perpendicular anisotropy facilitating its electrical readout and writing. Utilizing the unique nonlinear response and bipolar fading memory properties of the device, we demonstrate a multidimensional reservoir computing beyond the traditional binary paradigm. These results are expected to pave the way toward next-generation fast and massive neuromorphic computing.

Potential for multi-application advancements from doping zirconium (Zr) for improved optical, electrical, and resistive memory properties of zinc oxide (ZnO) thin films

Transition metal-doped Zinc oxide (ZnO) thin films with an optimal wide band gap and semiconducting nature find numerous applications in optoelectronic devices, gas sensors, spintronic devices, and electronics. In this study, Zirconium (Zr) doped ZnO thin films were deposited on ITO (Indium Tin oxide) coated glass substrate using RF-magnetron sputtering. Optical and electrical properties were examined for their potential use in resistive random-access memory (RRAM) applications. X-ray Diffraction (XRD), UV–vis spectroscopy, x-ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM) and Scanning electron microscopy (SEM) were used to investigate structural, optical, and compositional properties and roughness respectively. The results demonstrate that the films possess crystalline properties. Additionally, an augmentation in Zr concentration correlates with an elevation in the optical band gap, ascending from 3.226 eV to 3.26 eV, accompanied by an increase in Urbach energy from 0.0826 eV to 0.1234 eV. The film with the highest Zr content among all the films demonstrated the best electrical performance for resistive memory applications. Incorporating Zr as a dopant shows enhancement in the electrical performance and such ZnO films with optimum concertation of Zr can potentially be used in RRAM. ZnO being a versatile host material, its doping with Zr may extend its applications in catalysis, gas sensing, energy storage, and biomedical engineering. ZnO thin films employ zirconium (Zr) as a dopant, which is a novel way to improve the material’s characteristics. Although ZnO has been thoroughly researched, adding Zr presents a novel technique to enhance optical, electrical, and resistive memory characteristics all at once that has not been fully investigated.

UV-Mediated Facile Fabrication of a Robust, Fully Renewable and Controllably Biodegradable Poly(lactic acid)-Based Covalent Adaptable Network.

A robust and fully biobased covalent adaptable network (CAN) that allows recyclability, biocompatibility, and controlled biodegradability is reported. The CAN was fabricated through a simple photo-cross-linking method, wherein low-molecular-weight poly(lactic acid) (∼3 kDa) was modified with end 1,2-dithiolane rings through a one-step Steglich esterification reaction with thioctic acid (TA). These incorporated 1,2-dithiolane rings undergo photoinduced ring-opening polymerization, thus enabling the cross-linking of poly(lactic acid) with abundant dynamic disulfide bonds. The resultant CAN demonstrates excellent transparency, effective UV-blocking capabilities below 320 nm, robust tensile strength (∼39 MPa), and superior dimensional stability at 80 °C, alongside attractive biocompatibility. Moreover, owing to the dynamic exchange and redox-responsiveness of disulfide bonds, the material can be recycled by hot-pressing and a reduction-oxidation process while also being capable of controllably biodegrading at the end of its lifecycle. Furthermore, it exhibits reconfigurable shape memory properties with fast recovery. This study elucidates a straightforward approach to fabricating multifunctional and sustainable polymer materials with potential applications in diverse fields such as packaging, coating, and biomedicine.

Influence of Highly Charged Ion Irradiation on the Electrical and Memory Properties of Black Phosphorus Field‐Effect Transistors

Influence of Highly Charged Ion Irradiation on the Electrical and Memory Properties of Black Phosphorus Field‐Effect Transistors