Self-assembled multi-layered carbon nanofiber nanopaper for significantly improving electrical actuation of shape memory polymer nanocomposite

This study presents an effective approach to significantly improve the electrical properties of shape memory polymer (SMP) nanocomposites that show Joule heating triggered shape recovery. Carbon nanofibers (CNFs) were self-assembled to form multi-layered nanopaper to enhance the bonding and shape recovery behavior of SMP, respectively. It was found that both glass transition temperature (Tg) and electrical properties of the SMP nanocomposites have been improved by incorporating multi-layers of self-assembled nanopapers. The electrically actuated shape recovery behavior and the temperature profile during the actuation were monitored and characterized at a voltage of 30 V.     

Synergistic effect of siloxane modified aluminum nanopowders and carbon fiber on electrothermal efficiency of polymeric shape memory nanocomposite

The present study reports an effective approach of significantly enhancing electrothermal efficiency and shape recovery performance of shape memory polymer (SMP) nanocomposite, of which shape recovery was induced by electrically resistive heating. Metallic aluminum (Al) nanopowders synthesized from Al³⁺ solution were chemically grafted onto carbon fiber. Siloxane groups were grafted onto surfaces of the Al nanopowders to enhance the interfacial bonding between the carbon fiber and SMP matrix via van der Waals force and covalent bond, respectively. The siloxane modified Al surfaces could improve both the electrically induced shape recovery performance and electrothermal efficiency through facilitating the electrically resistive heating from carbon fiber into the SMP matrix. Effectiveness of the synergistic effect between siloxane modified Al surface and carbon fiber was demonstrated to achieve the electrical actuation for SMP nanocomposites at a low electrical voltage below 4.0 V.     

Surface coating of multi-walled carbon nanotube nanopaper on shape-memory polymer for multifunctionalization

We are presenting a method of synthesizing three-dimensional self-assembled multi-walled carbon nanotube (MWCNT) nanopaper on hydrophilic polycarbonate membrane. The process is based on the very well-defined dispersion of nanotube and controlled pressure vacuum deposition procedure. The morphology and structure of the nanopaper are characterized with scanning electronic microscopy (SEM) over a wide range of scale sizes. A continuous and compact network observed from the microscopic images indicates that the MWCNT nanopaper could have highly conductive property. As a consequence, the sensing properties of conductive MWCNT nanopaper are characterized by functions of temperature and water content. Meanwhile, in combination with shape-memory polymer (SMP), the conductive MWCNT nanopaper facilitates the actuation in SMP nanocomposite induced by electrically resistive heating. Furthermore, the actuating capability of SMP nanocomposite is utilized to drive up a 5-gram mass from 0 to 30 mm in height.     

纤维增强形状记忆聚合物复合材料及其航天应用

形状记忆聚合物(SMP)是一种能够保持临时形状,并在外界刺激下自发回复到其初始形状的智能材料,具有高形状固定率、高形状回复率、转变温度可调、变形能力强、质量轻等优点,但其应用受到响应方式单一和承载能力差的限制,通过向聚合物中添加功能颗粒或增强纤维制成形状记忆聚合物复合材料(SMPC),可有效解决这一问题。首先介绍了SMP形状记忆效应的原理,然后阐述了纤维增强型SMPC有限变形过程中纤维的微屈曲行为。最后对可变形结构在航天领域的应用进行了论述。      

Effect of fiber arrangement on shape fixity and shape recovery in thermally activated shape memory polymer-based composites

In the present study, we conducted periodic-cell simulations of the thermomechanical cycle of thermally activated shape memory polymer (SMP)-based composites. The present simulation utilizes a micromechanical model for reproducing the discontinuous fibers and SMP. We analyzed the effect of fiber volume fraction, fiber aspect ratio, and fiber end position on the shape fixity and shape recovery of the composite. The simulated results revealed that fiber elasticity is a key factor for the shape fixity of the composite, while both strain concentration near the fiber ends and fiber elasticity play important roles in the shape recovery properties of the composite.     

Significantly improving infrared light-induced shape recovery behavior of shape memory polymeric nanocomposite via a synergistic effect of carbon nanotube and boron nitride

The present work studies the thermomechanical properties and infrared light-induced shape memory effect (SME) in shape memory polymer (SMP) nanocomposite incorporated with carbon nanotube (CNT) and boron nitride. The combination of CNT and boron nitride results in higher glass transition temperature, mechanical strength and thermomechanical strength. While CNTs are employed to improve the absorption of infrared light and thermally conductive property of SMP, boron nitrides facilitate heat transfer from CNTs to the polymer matrix and thus to enable fast response. A unique synergistic effect of CNT and boron nitride was explored to facilitate the heat transfer and accelerate the infrared light-induced shape recovery behavior of the shape memory polymeric nanocomposite.     

Synthesis and characterization of a novel biodegradable thermoplastic shape memory polymer

A novel poly(urethane-urea) shape memory polymer (PUU SMP) was synthesized from poly(DL-lactic acid) (PDLLA) Diols, hexamethylene diisocyanate(HDI) and butanediamine(BDA), aiming to develop a biodegradable and biocompatible shape memory polymer. Its structure, thermal properties and shape-memory behaviors were characterized through Fourier transform infrared spectrometry (FTIR), differential scanning calorimetry (DSC) and bending test. The results showed that the response temperature for shape memory of PDLLA–PUU SMP is dependent on the polymeric glass transition temperature and this polymer has an excellent shape memory effect, having the ratio of the shape-memory fixation approximately 100% and the ratio of the shape-memory recovery about 98%.     

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.     

Mechanical and radiographic properties of a shape memory polymer composite for intracranial aneurysm coils

An intracranial aneurysm can be a serious condition that can go undetected until the aneurysm ruptures, causing hemorrhaging within the subarachnoid space surrounding the brain. The typical treatment for large aneurysms is by embolization using platinum coils. However, in about 15% of the cases treated by platinum coils, the aneurysm eventually re-opens as a result of the bio-inertness of platinum. One solution to this is to develop suitable materials with increased bio-activity to use as coil implants. In this research, a shape memory polymer (SMP), Calomer™, produced by The Polymer Technology Group, Inc., was investigated as a candidate for aneurysm coils. The SMP was tested to determine its thermo-mechanical properties and the strength of the shape recovery force. Composite SMP specimens containing tantalum filler were produced and tested to determine the mechanical effect of adding this radio-opaque metal. Thermo-mechanical testing showed that the material exhibited a shape recovery force a few degrees above the glass transition temperature, T_g. The effects of the addition were small and included a decrease in T_g and recovery force. SMP coils deployed inside a simulated aneurysm model demonstrate that typical hemodynamic forces do not hinder the shape recovery process. The radio-opacity of the Ta-filled material was characterized with clinical fluoroscopy.     

Analysis and design of smart mandrels using shape memory polymers

Based on the thermomechanical mechanism of shape memory polymers (SMPs), the three-dimensional thermomechanical constitutive equation that can be used in the ABAQUS finite element simulation was derived. Then this paper compiled UMAT subroutine and simulated the thermomechanical behaviors of SMP smart mandrels. In addition, the properties of shape fixity and shape recovery ratio of SMP were considered in detail. Finally, filament winding experiments were proceeded on bottle-shaped and air duct-shaped mandrels and the simple and efficient demoulding of SMP mandrels were verified. The results showed the feasibility of SMP as the smart mandrels from practical application in the future.     

A review of shape memory polymer composites and blends

Shape memory polymers (SMPs) are a kind of very important smart polymers. In order to improve the properties or obtain new functions of SMPs, SMP composites and blends are prepared. We thoroughly examine the research in SMP composites and blends achieved by numerous research groups around the world. The preparation of SMPs composites and blends is mainly for five aims: (1) to improve shape recovery stress and mechanical properties; (2) to decrease shape recovery induction time by increasing thermal conductivity; (3) to create new polymer/polymer blends with shape-memory effect (SME); (4) to tune switch temperature, mechanical properties, and biomedical properties of SMPs; (5) to fabricate shape memory materials sensitive to electricity, magnetic, light and moisture. The trend of SMP composite development is discussed. SMP composites and blends exhibit novel properties that are different from the conventional SMPs and thus can be utilized in various applications.     

On the cyclic material stability of shape memory polymer

This paper presents the experimental study of a Thermoplastic Polyurethane (TPU) based Shape Memory Polymer (SMP) produced from granulates of commercially available Estane^TM ETE75DT3 NAT022 (Oevel Westerlo, Belgium). This polymer is characterized by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Thermal Analysis (DMTA). The experimental procedure was designed to study the functional properties (shape fixity and shape recovery) of this shape memory polymer in multiple programming/shape‐recovery cycles at three different programming temperatures. The results are displayed in the temperature‐stress‐strain space with focus on parameters which characterize the functional fatigue and material stability of the tested polymer during consecutive cycles. These results give a better understanding of this material class that has a potential for actuator applications in engineering.     

A 3D finite deformation constitutive model for amorphous shape memory polymers: A multi-branch modeling approach for nonequilibrium relaxation processes

Shape memory polymers (SMPs) are materials that can recover a large pre-deformed shape in response to environmental stimuli. For a thermally activated amorphous SMP, the pre-deformation and recovery of the shape require the SMP to traverse its glass transition temperature (T_g) to complete the shape memory (SM) cycle. As a result, the recovery behavior of SMPs shows strong dependency on both the pre-deforming temperature and recovery temperature. Generally, to capture the multitude of relaxation processes, multi-branch models (similar to the 1D generalized viscoelastic model or Prony series) are used to model the time-dependent behaviors of polymers. This approach often requires an arbitrary (usually numerous) number of branches to capture the material behavior, which results in a substantial number of material parameters. In this paper, a multi-branch model is developed to capture the SM effect by considering the complex thermomechanical properties of amorphous SMPs as the temperature crosses T_g. The model utilizes two sets of nonequilibrium branches for fundamentally different modes of relaxation: the glassy mode and Rouse modes. This leads to a significant reduction in the number of material parameters. Model simulation comparisons with a range of thermomechanical experiments conducted on a tert-butyl acrylate-based SMP show very good agreement. The model is further utilized to explore the intrinsic recovery behavior of an SMP and the size effects on the free recovery characteristics of a magneto-sensitive SMP composite.     

Electrically Controlled Nano and Micro Actuation in Memristive Switching Devices with On‐Chip Gas Encapsulation

Nanoactuators are a key component for developing nanomachinery. Here, an electrically driven device yielding actuation stresses exceeding 1 MPa withintegrated optical readout is demonstrated. 10 nm thick Al₂O₃ electrolyte films are sandwiched between graphene and Au electrodes. These allow reversible room‐temperature solid‐state redox reactions, producing Al metal and O₂ gas in a memristive‐type switching device. The resulting high‐pressure oxygen micro‐fuel reservoirs are encapsulated under the graphene, swelling to heights of up to 1 µm, which can be dynamically tracked by plasmonic rulers. Unlike standard memristors where the memristive redox reaction occurs in single or few conductive filaments, the mechanical deformation forces the creation of new filaments over the whole area of the inflated film. The resulting on–off resistance ratios reach 10⁸ in some cycles. The synchronization of nanoactuation and memristive switching in these devices is compatible with large‐scale fabrication and has potential for precise and electrically monitored actuation technology.     

Shape memory and thermo-mechanical properties of shape memory polymer/carbon fiber composites

In this study, chopped carbon fiber reinforced trans-1, 4-polyisoprene (TPI) was developed via a proposed new manufacturing process with the aim of improving weak mechanical properties of bulk TPI bulk. Specimens of the developed shape memory polymer (SMP) composites were fabricated with carbon fiber weight fraction of 5%, 7%, 9%, 11% and 13%, respectively. Measured are the effects of chopped carbon fiber and temperature on: (a) shape recovery ratio and rate; (b) stress–strain relationship; (c) maximum tensile stress, strain and Young’s modulus; and (d) maximum stress and residual strain under a constant strain cyclic loading. In addition, SEM micrographs were also presented to illustrate the fracture surface. The present experimental results show that the SMP with 7% carbon fiber weight fraction appears to perform best in all the tests. This indicates that the 7% carbon fiber weight fraction could be the optimum value for the SMP developed using the proposed manufacturing process.     

Modulated interaction in double-layer shape memory-based micro-designed actuators

The effect of superposed transitions in actuators with layered shape memory alloy (SMA) films undergoing martensitic phase transformation is analyzed in terms of a model developed for two layers of different composition, deposited at the same temperature on a substrate. A significant difference is observed in the actuation versus temperature relationship, depending on the thermal and elastic properties of the SMA layers and their martensitic transformation temperature. The prediction of the actuation is exemplified using a multilayer model and is verified for a cantilever actuator with NiTi and NiMnGa layers deposited on a Si substrate. The model sets the ground for a smart selection of SMAs in order to achieve a modulated actuation.     

纤维素/琼脂糖复合膜的制备、表征及其形状记忆性能研究

近年来,形状记忆材料因其刺激响应性在纺织、航空航天、生物医疗等领域备受关注。在此,采用碱/尿素水溶液作为共溶剂,环氧氯丙烷作为交联剂,制备出具有水、热刺激形状记忆性能的纤维素/琼脂糖复合膜。该膜显示出良好的透明度和力学性能,透光率超过90%,干强和湿强可达132和5.4 MPa。同时,该膜在水刺激下的固定率(R_f)和回复率(R_r)分别达95%和84%以上,热刺激下的R_f和R_r分别达58%和85%以上,表现出较好的形状记忆效果。机理分析表明:氢键的断裂和形成导致复合膜具有水刺激形状记忆行为,琼脂糖结晶的破坏与形成是复合膜具有热刺激形状记忆行为的关键。     

Modulated interaction in double-layer shape memory-based micro-designed actuators

Abstract

The effect of superposed transitions in actuators with layered shape memory alloy (SMA) films undergoing martensitic phase transformation is analyzed in terms of a model developed for two layers of different composition, deposited at the same temperature on a substrate. A significant difference is observed in the actuation versus temperature relationship, depending on the thermal and elastic properties of the SMA layers and their martensitic transformation temperature. The prediction of the actuation is exemplified using a multilayer model and is verified for a cantilever actuator with NiTi and NiMnGa layers deposited on a Si substrate. The model sets the ground for a smart selection of SMAs in order to achieve a modulated actuation.     

Electrical properties of carbon-containing epoxy compositions under shape memory effect realization

The behavior of electrical resistance R of compression-deformed samples of the epoxy polymer-thermoexpanded graphite (EP-TEG) and EP-TEG-kaolin compositions has been investigated in the shape recovery temperature range. It is shown that the process of shape recovery is accompanied by a jump-like increase of R related to the sample length change. The addition of kaolin decreases the absolute value of electrical resistivity of the deformed polymer compositions and increases the value of R jump. The revealed changes in R are explained with the attraction of data on differential scanning calorimetry (DSC) measurements, results of investigations of composite microstructure and percolation model representations.     

Electroactive shape memory polymer based on optimized multi-walled carbon nanotubes/polyvinyl alcohol nanocomposites

The development of shape memory polymers (SMPs) has gained remarkable attention due to their wide range of applications, from biomedical to electromechanical. In this work, we have developed and optimized an electroactive SMP based on polyvinyl alcohol/multi-walled carbon nanotubes (PVA/MWNTs) composites. When a constant voltage of 60 V was applied to the optimized sample, the polymer shape could be recovered to the original form within 35 s. Different weight fractions of MWNT/PVA composites were prepared by using a simple solution blending and transitional solution casting method, and their microstructures, electrical conductivities, thermal conductivities, and electroactive shape memory properties were investigated. According to our systematic analysis, the enhanced performance can be attributed to the reinforcement of MWNTs that led to the improved electrical and thermal conductivities of the PVA matrix.