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.     

Controlling Au electrode patterns for simultaneously monitoring electrical actuation and shape recovery in shape memory polymer

This paper presents an effective approach to achieve efficient electrical actuation and monitoring of shape recovery based on patterned Au electrodes on shape memory polymer (SMP). The electrically responsive shape recovery behavior was characterized and monitored by the evolution change in electrical resistance of patterned Au electrode. Both electrical actuation and temperature distribution in the SMP have been improved by optimizing the Au electrode patterns. The electrically actuated shape recovery behavior and temperature evolution during the actuation were monitored and characterized. The resistance changes could be used to detect beginning/finishing points of the shape recovery. Therefore, the Au electrode not only significantly enhances the electrical actuation performance to achieve a fast electrical actuation, but also enables the resistance signal to detect the free recovery process.     

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.     

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.     

Preparation and properties of poly (p-phenylene sulfide)/multiwall carbon nanotube composites obtained by melt compounding

In this paper, electrical and mechanical properties of Poly (p-phenylene sulfide) (PPS)/multi-wall carbon nanotubes (MWNTs) nanocomposites were reported. The composites were obtained just by simply melt mixing PPS with raw MWNTs without any pre-treatment. The dispersion of MWNTs and interfacial interaction were investigated through SEM &TEM and Raman spectra. The rheological test and crystallization behavior were also investigated to study the effects of MWNTs concentration on the structure and chain mobility of the prepared composites. Though raw MWNTs without any pre-treatment were used, a good dispersion and interaction between PPS and MWNTs have been evidenced, resulting in a great improvement of electrical properties and mechanical properties of the composites. Raman spectra showed a remarkable decrease of G band intensity and a shift of D bond, demonstrating a strong filler–matrix interaction, which was considered as due to π–π stacking between PPS and MWNTs. The storage modulus (G′) versus frequency curve presented a plateau above the percolation threshold of about 2–3 wt% with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behavior. Meanwhile, a conductive percolation threshold of 5 wt% was achieved and the conductivity of nanocomposites increased sharply by several orders of magnitude. The difference between electrical and rheological percolation threshold, and the effect of critical percolation on the chain mobility, especially on crystallization behavior of PPS, were discussed. In summary, our work provides a simple and fast way to prepare PPS/MWNTs nanocomposites with good dispersion and improved properties.     

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.     

Electrical resistance change and crack behavior in carbon nanotube/polymer composites under tensile loading

This paper studies the electrical and mechanical responses of cracked carbon nanotube (CNT)-based polymer composites. Tensile tests were performed on single-edge cracked plate specimens of the nanocomposites at room temperature and liquid nitrogen temperature (77 K), and the electrical resistance change of the specimens was monitored. An analytical model based on the electrical conduction mechanism of CNT-based composites was also developed to predict the resistance change resulted from crack propagation. The crack induced resistance change was calculated, and a comparison of the analytical predictions against the experimental data was made to validate the applicability of the model. In addition, the fracture properties of the nanocomposites were assessed in terms of the J-integrals using an elastic-plastic finite element analysis.     

Facile preparation,characterization and performance of noncovalently functionalized graphene/epoxy nanocomposites with poly(sodium 4-styrenesulfonate)

Graphene was noncovalently functionalized with poly(sodium 4-styrenesulfonate) (PSS) and then successfully incorporated into the epoxy resin via in situ polymerization to form functional and structural nanocomposites. The morphology and structure of PSS modified graphene (PSS-g) were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The effects of PSS-g additions on tensile, electrical and thermal properties of the epoxy/graphene nanocomposites were studied. Noncovalent functionalization improved interfacial bonding between the epoxy matrix and graphene, leading to enhanced tensile strength and modulus of resultant nanocomposites. The PSS-g additions also enhanced electrical properties of the epoxy/PSS-g nanocomposites, resulting in a lower percolation threshold of 1.2 wt%. Thermogravimetric and differential scanning calorimetric results showed the occurrence of a two-step decomposition process for the epoxy/PSS-g nanocomposites.     

Effects of grafted chain length on mechanical and electrical properties of nanocomposites containing polylactide-grafted carbon nanotubes

We herein report the effects of interfacial reinforcement on mechanical and electrical properties of nanocomposites based on polylactide (PLA) and multi-walled carbon nanotube (MWCNT). For this purpose, a series of MWCNTs grafted with PLA chains of various lengths (MWCNT-g-PLAs) were prepared by ring-opening polymerization of l-lactide with carboxylic acid-functionalized MWCNT (MWCNT-COOH). MWCNT-g-PLAs were then mixed with commercial PLA to obtain PLA/MWCNT-g-PLA nanocomposites with 1.0 wt.% MWCNT content. It was revealed that morphological, mechanical, and electrical properties of PLA/MWCNT-g-PLA nanocomposites were strongly dependent on the PLA chain length of MWCNT-g-PLAs. FE-SEM images exhibited that the nanocomposites containing MWCNT-g-PLA with longer PLA chain length exhibited better dispersion of MWCNTs in the PLA matrix. Initial moduli and tensile strengths of PLA/MWCNT-g-PLA composites increased with the increment of chain length of PLA grafted on MWCNTs, which attributes to the improved interfacial adhesion between the grafted PLA chains of MWCNT-g-PLA and the PLA matrix. As a result, the experimental initial modulus (2775 ± 193 MPa) of the nanocomposite including MWCNT-g-PLA with PLA chains of average molecular weight of 530 g/mol was quite close to the theoretical value (2911 MPa) predicted for the nanocomposite with perfect interfacial adhesion. Unexpectedly, electrical resistivities of PLA/MWCNT-g-PLA nanocomposites were found to increase from ∼10⁴ to ∼10¹² Ω/sq with increasing the PLA chain length of MWCNT-g-PLA, which is due to the fact that the PLA chains grafted on MWCNTs prevent the formation of the electrical conduction path of MWCNTs in the PLA matrix.     

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.     

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.     

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.     

Synthesis and characterization of novel waterborne polyurethane nanocomposites with magnetic and electrical properties

The novel nanocomposites derived from waterborne polyurethane and nano-Fe₃O₄ (WPU/Fe₃O₄) have been successfully synthesized by in situ polymerization progress. The nano-Fe₃O₄ particles prepared by co-precipitation method were modified by using oleic acid (OA) to improve their compatibility with monomers. The chemical structures, morphology, thermal behavior, mechanical properties, magnetic properties and electrical properties of the WPU/Fe₃O₄ nanocomposites were investigated by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscope (AFM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), vibrating sample magnetometer (VSM) and high resistance meter respectively. The results indicated that the Fe₃O₄ nanoparticles modified by oleic acid could be homogeneously dispersed in the WPU and the introduction of ones was obviously improving the thermal properties, magnetic properties and electrical properties of WPU/Fe₃O₄ nanocomposites. The resulting WPU/Fe₃O₄ nanocomposites would be having the potential applications in microwave absorption.     

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.     

The effective properties and local aggregation effect of CNT/SMP composites

A micromechanics model of the thermomechanical constitutive behavior and micro-structural inhomogeneity of carbon nanotubes (CNTs)/shape memory polymer (SMP) composites is presented. It is assumed that the CNTs are elastic and the SMP obeys a thermomechanical constitutive law. The effective properties of CNT/SMP composites are examined using a micro-mechanics method. The effect of CNT aggregation in the composite, frequently encountered in real engineering situations, is studied. The degree of aggregation is described by an aggregation coefficient, and the effective properties of SMP composites with aggregated CNTs are calculated using a stepping scheme. It is shown that the degree of CNT aggregation dramatically influences the effective properties of the CNT/SMP composites. A homogeneous microstructure leads to maximum levels of effective composite properties.     

Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites

The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T_g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T_g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control.     

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.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Dielectric anisotropy and electrical properties of the copper phthalocyanine (CuPc): 4–4′-n-Heptylcyanobiphenyl (7CB) composite liquid crystals

Dielectric anisotropy and electrical properties of the copper phthalocyanine (CuPc): 4–4′-n-heptylcyanobiphenyl (7CB) composite liquid crystals have been investigated. Liquid crystals exhibit dielectrically-controlled positive dielectric anisotropy (p-type Δɛ) and the dielectric anisotropy changes from positive to negative dielectric anisotropy (n-type Δɛ) behavior with frequency of applied electrical field. The critical frequency f_c values for the 7CB and CuPc doped 7CB liquid crystals were found to be 602 kHz and 518 kHz, respectively. This indicates that CuPc doping causes a decrease in the critical frequency. The splay elastic coefficients of the 7CB and CuPc doped 7CB liquid crystals were determined and CuPc doping increases the splay elastic coefficient of 7CB liquid crystal. The 7CB liquid crystal exhibits a voltage-controlled differential negative resistance (VCNR) behavior and CuPc doping affects significantly VCNR behavior of 7CB.     

Structural and magnetic properties of nanocomposites based on nanostructured polyaniline and titania nanotubes

Nanocomposites consisting of self-assembled polyaniline (PANI) nanostructures and titania nanotubes (TiO₂-NT) were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous dispersion of TiO₂-NT (outer diameter ~10 nm), without added acid. The influence of initial mole ratio of aniline to TiO₂ (80, 20, and 5) on the morphology, electrical conductivity, molecular structure, crystallinity, and magnetic properties of synthesized PANI/TiO₂ nanocomposites was studied. Transmission electron microscopy, Raman spectroscopy, and X-ray powder diffraction proved that the shape and structure of TiO₂-NT in the final nanocomposites were preserved. The shape of PANI nanostructures formed in the nanocomposites was influenced by the initial aniline/TiO₂-NT mole ratio. Nanotubes and nanorods are predominant PANI nanostructures in the nanocomposite prepared with the highest aniline/TiO₂ mol ratio of 80. The decrease of aniline/TiO₂ molar ratio induced more pronounced formation of nanorod network. The electrical conductivity of PANI/TiO₂ nanocomposites was in the range (1.3–2.4) × 10^?3 S cm^?1. The nanocomposites exhibit weak ferromagnetic behavior. Approximately order of magnitude lower values of coercive field and remanent magnetization were obtained for nanocomposite samples in comparison to pure PANI.