Development of 3D-Printed,Biodegradable, Conductive PGSA Composites for Nerve Tissue Regeneration

Nerve conduits are used to reconnect broken nerve bundles and provide protection to facilitate nerve regeneration. However, the low degradation rate and regeneration rate, as well as the requirement for secondary surgery are some of the most criticized drawbacks of existing nerve conduits. With high processing flexibility from the photo-curability, poly (glycerol sebacate) acrylate (PGSA) is a promising material with tunable mechanical properties and biocompatibility for the development of medical devices. Here, polyvinylpyrrolidone (PVP), silver nanoparticles (AgNPs), and graphene are embedded in biodegradable PGSA matrix. The polymer composites are then assessed for their electrical conductivity, biodegradability, three-dimensional-printability (3D-printability), and promotion of cell proliferation. Through the four-probe technique, it is shown that the PGSA composites are identified as highly conductive in swollen state. Furthermore, biodegradability is evaluated through enzymatic degradation and facilitated hydrolysis. Cell proliferation and guidance are significantly promoted by three-dimensional-printed microstructures and electrical stimulation on PGSA composites, especially on PGSA-PVP. Hence, microstructured nerve conduits are 3D-printed with PGSA-PVP. Guided cell growth and promoted proliferation are subsequently demonstrated by Schwann cell culture combined with electrical stimulation. Consequently, 3D-printed nerve conduits fabricated with PGSA composites hold great potential in nerve tissue regeneration through electrical stimulation.     

Potential use of NR and wood/NR composites as thermal neutron shielding materials

This work investigated thermal neutron shielding, cure characteristics and mechanical properties of natural rubber (NR) and wood/NR composites with addition of either boron oxide (B₂O₃) or boric acid (H₃BO₃) for potential use as flexible shielding materials. The results showed that increase in the B₂O₃ or H₃BO₃ content from 0 to 80 phr and 0–50 phr in 10-phr increments, respectively, could improve thermal neutron shielding properties but reduced overall tensile properties, while the addition of 20-phr wood particles in wood/NR composites improved surface hardness and dimensional stability. Furthermore, the values of the Half Value Layer (HVL), which represent the required thickness of material to attenuate half of the incoming neutrons, were evaluated at a content of 80-phr B₂O₃ by varying thickness of both NR and wood/NR composites from 2.5 mm to 20.0 mm in 2.5-mm increments. The results indicated that the HVL values were approximately the same at 3.5 mm. Hence, the overall properties investigated in this work suggested great potential of these composites to be used as effective thermal neutron shielding materials.     

Styrenated phenol modified nanosilica for improved thermo-oxidative and mechanical properties of natural rubber

The present work aims to prepare thermal and oxidation resistant Natural Rubber (NR) composites using antioxidant-modified nanosilica (MNS). The thermo-oxidative aging performance of the composites was evaluated by the variations in mechanical properties after aging at 100 °C for 24 h. The performance was further monitored through Scanning Electron Microscopy, Fourier Transform Infrared spectroscopy, Thermogravimetric Analysis, and Dynamic Mechanical Analysis. NR nanocomposite with 1–7.5 phr nanosilica (NS) and 3 phr MNS were prepared and its rheological properties were studied. A comparative study of the theoretical models yielded that modified Guth-Gold equation predicted Young's modulus better than other models. Thermal stability of natural rubber MNS composite was improved by 10 °C with pre-eminent mechanical properties like tensile strength and heat build-up. A linear relationship of compression set with modulus of all composites were also established. Equilibrium swelling test revealed improved crosslink density in NR MNS composite. The strong interaction between antioxidant and nanosilica enabled low migration of antioxidant in NR MNS composite. Hence its protective function after aging showed more effective than NR NS composites. These versatile functional properties of NR MNS composite suggest its potential application in electrical, electronic and high performance rubber products.     

Vapor deposition of ultrathin hydrophilic polymer coatings enabling candle soot composite for highly sensitive humidity sensors

Candle soot (CS) is a desirable carbon nanomaterial for sensors owing to its highly porous nanostructure and large specific surface area. CS is advantageous in its low-cost and facile preparation compared to graphene and carbon nanotubes, but its pristine nanostructure is susceptible to collapse, hampering its application in electronic devices. This article reports conformal coating of nanoscale crosslinked hydrophilic polymer on CS film using initiated chemical vapor deposition, which well preserved the CS nanostructure and obtained nanoporous CS@polymer composites. Tuning coating thickness enabled composites with different morphologies and specific surface areas. Surprisingly, the humidity sensor made from composite with the lowest filling degree, thus largest specific surface area, showed relatively low sensitivity, which is likely due to its discontinuous structure, thus insufficient conductive channels. Composite sensor with optimum filling degree shows excellent sensing response of more than 10³ with the linearity of R² = 0.9400 within a broad relative humidity range from 11% to 96%. The composite sensor also exhibits outstanding sensing performance compared to literature with low hysteresis (3.00%), a satisfactory response time (28.69 s), and a fast recovery time (0.19 s). The composite sensor is fairly stable and durable even after 24 h soaking in water. Furthermore, embedding a humidity sensor into a face mask realizes real-time monitoring of human breath and cough, suggesting promising applications in respiratory monitoring.     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

Flexible,stretchable and conductive PVA/PEDOT:PSS composite hydrogels prepared by SIPN strategy

Stretchable conductive hydrogels have received significant attention due to their possibility of being utilized in wearable electronics and healthcare devices. In this work, a semi-interpenetrating polymer network (SIPN) strategy was employed to fabricate a set of flexible, stretchable and conductive composite hydrogels composed of polyvinyl alcohol (PVA) in the presence of glutaraldehyde as the crosslinker, HCl as the catalyst and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) as the conductive medium. The results from FTIR, Raman, SEM and TGA indicate that a chemical crosslinking network and interactions of PVA and PEDOT:PSS exist in the SIPN hydrogels. The swelling ratio of hydrogels decreased with increasing content of PEDOT:PSS. Due to the chemical crosslinking network and interactions of PVA and PEDOT:PSS, PVA networks semi-interpenetrated with PEDOT:PSS exhibited excellent tensile and compression properties. The tensile strength and elongation at breakage of the composite hydrogels with 0.14 wt% PEDOT:PSS were 70 KPa and 239%, respectively. The compression stress of the composite hydrogels with 0.14 wt% PEDOT:PSS at a strain of 50% was about 216 KPa. The electrical conductivity of the hydrogels increased with increasing PEDOT:PSS content. The flexible, stretchable and conductive properties endow the composite hydrogel sensor with a superior gauge factor of up to 4.4 (strain: 100%). Coupling the strain sensing capability to the flexibility, good mechanical properties and high electrical conductivity, we consider that the designed PVA/PEDOT:PSS composite hydrogels have promising applications in wearable devices, such as flexible electronic skin and sensitive strain sensors.     

Printing graphene-carbon nanotube-ionic liquid gel on graphene paper: Towards flexible electrodes with efficient loading of PtAu alloy nanoparticles for electrochemical sensing of blood glucose

The increasing demands for portable, wearable, and implantable sensing devices have stimulated growing interest in innovative electrode materials. In this work, we have demonstrated that printing a conductive ink formulated by blending three-dimensional (3D) porous graphene–carbon nanotube (CNT) assembly with ionic liquid (IL) on two-dimensional (2D) graphene paper (GP), leads to a freestanding GP supported graphene–CNT–IL nanocomposite (graphene–CNT–IL/GP). The incorporation of highly conductive CNTs into graphene assembly effectively increases its surface area and improves its electrical and mechanical properties. The graphene–CNT–IL/GP, as freestanding and flexible substrates, allows for efficient loading of PtAu alloy nanoparticles by means of ultrasonic-electrochemical deposition. Owing to the synergistic effect of PtAu alloy nanoparticles, 3D porous graphene–CNT scaffold, IL binder and 2D flexible GP substrate, the resultant lightweight nanohybrid paper electrode exhibits excellent sensing performances in nonenzymatic electrochemical detection of glucose in terms of sensitivity, selectivity, reproducibility and mechanical properties.     

Effect of surface treatment with potassium permanganate on ultra-high molecular weight polyethylene fiber reinforced natural rubber composites

The effects of surface treatment using potassium permanganate on ultra-high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were investigated. The results showed the surface roughness and the oxygen-containing groups on the surface of the modified fibers were effectively increased. The NR matrix composites were prepared with as-received and modified UHMWPE fibers added 0–6 wt%. The treated fibers increased the modulus and tensile stress at a given elongation. The tear strength increased with increasing fiber mass fraction, attained maximum values at 4 wt%. The hardness of composites exhibited continuous increase with increasing the fiber content. The dynamic mechanical tests showed that the storage modulus and the tangent of the loss angle were decreased in the modified UHMWPE fibers/NR composites. Several micro-fibrillations between the treated fiber and NR matrix were observed, which meant the interfacial adhesion strength was improved.     

Development and investigation of the flexible hydrogen sensor based on ZnO-decorated Sb2O3 nanobelts

Hydrogen is regarded as the next-gen fuel for vehicles to avoid the emission of toxic gases, which needs a continuous monitoring of the concentration level. In the design of the H₂ sensor, especially of flexible type, a sensing layer will be blended, which affects the sensing performance of the device. Based on this concern, the present investigation is carried out to understand the effect of the bending angle toward the sensing performance of bare and ZnO (n-type)-decorated Sb₂O₃ (p-type) nanobelt–based sensors for hydrogen gas. The sensing element was prepared by the thermal chemical vapor deposition followed by the drop-casting method. Furthermore, the role of the zinc precursor (molar concentration—1 M–3 M) on the preparation of ZnO-decorated Sb₂O₃ nanobelts was studied. Various techniques were used to confirm the formation of ZnO-decorated nanobelts such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), and Fourier transform infrared spectroscopy (FTIR). From these analyses, 1 M concentration of the zinc precursor shows uniform distribution of nanoparticles over the surface of Sb₂O₃ nanobelts. However, agglomeration was observed when the concentration of the zinc precursor increases from 1 M to 3 M. Later, the prepared nanobelts were deposited on the OverHead Projector (OHP) sheet by the doctor blade method for sensing hydrogen gas at 100 °C at a concentration of 1000–3000 ppm. In addition to it, the effect of the substrate bending angle (0°, 45°, 60°, and 90°) was analyzed at a fixed concentration of H₂ gas (1000 ppm). From this study, it is clear that the highest sensing response was achieved for 1 M decorated nanobelts compared with bare as well as other concentrations because of uniform distribution of nanoparticles on the surface of nanobelts. Moreover, the prepared sample demonstrates better sensing performance with the bending of substrates, which suggests that the prepared sensor could be used for flexible electronic devices. The prepared nanobelts show a good H₂ gas–sensing response even with bending of the substrates. The work suggests that the prepared sensor is applicable for flexible electronic devices.     

Effects of Sericite Modified by Macromolecular Dispersant on the Thermal,Mechanical and Electrical Properties of the NR/SBR Composites

A new hydrosoluble macromolecular dispersant and modifier, poly(ethylene glycol)-maleic anhydride-acrylic acid (PEG-MA-AA) terpolymer was synthesized via ring-opening reaction and free radical polymerization. The chemical structure of the PEG-MA-AA terpolymer was confirmed by Fourier transform infrared (FTIR) spectra and nuclear magnetic resonance spectroscopy (NMR), and its average molecular weight was determined by gel permeation chromatography (GPC). Modified sericite (MSE) was synthesized from sericite (SE) by the surface modification with PEG-MA-AA. The NR/SBR/MSE composites were prepared via the blending of the modified sericite and NR/SBR rubber. The thermal, mechanical and electrical properties of the composites were investigated by TGA, tensile test machine and high-insulation resistance meter. The results showed that the thermal stability and the mechanical and electrical insulation properties of NR/SBR/MSE composites were improved significantly. SEM also revealed that modified sericite possessed good dispersibility.     

Natural rubber composites reinforced with basic magnesium oxysulfate whiskers: Processing and ultraviolet resistance/flame retardant properties

The Magnesium sulfate whiskers (MOSw) were first modified by Stearic acid or Si69, and Natural rubber (NR)/modified-MOSw composites were prepared by blending the modified-MOSw with natural rubber latex. By adding modified-MOS_W into NR, the mechanical properties, the anti-ultraviolet aging property, flammability, and thermal stability of composites were improved obviously. The mechanical properties, crosslink density and thermal stability of composites reach the highest value at 4 wt% Si69-MOS_W. The composite with MOS_W addtion had a higher retention rate after ultraviolet irradiation and the MOS_W could improve the anti-ultraviolet aging property of rubber matrix. The modified MOS_W can effectively improve the oxygen index and the flame retardant grade of rubber composites.     

Polyaniline-coated coconut fibers: Structure,properties and their use as conductive additives in matrix of polyurethane derived from castor oil

Electrically conducting fibers based on coconut fibers (CF) and polyaniline (PANI) were prepared through in situ oxidative polymerization of aniline (ANI) in the presence of CF using iron (III) chloride hexahydrate (FeCl_3.6H₂O) or ammonium persulfate (APS) as an oxidant. The PANI-coated coconut fibers (CF-PANI) displayed various morphologies, electrical conductivities and percentages of PANI on the CF surface. For both systems, a PANI conductive layer was present on the CF surface, which was responsible for an electrical conductivity of around 1.5 × 10⁻¹ and 1.9 × 10⁻² S cm⁻¹ for composites prepared with FeCl₃.6H₂O and APS, respectively; values that are similar to that of pure PANI. In order to modify the structure and properties of polyurethane derived from castor oil (PU) both CF-PANI and pure PANI were used as conductive additives. The PU/CF-PANI composites exhibited higher electrical conductivity than pure PU and PU/PANI blends. Additionally, the PU/CF-PANI composites showed a variation in electrical resistivity according to the compressive stress applied, indicating that these materials could be applied for pressure-sensitive applications.     

Novel biphasic structured composite prepared by in situ silica filling in natural rubber latex

The sol‐gel reaction of tetraethoxysilane in natural rubber (NR) latex was conducted to produce in situ silica‐filled NR latex, followed by adding sulfur cross‐linking reagents to the latex in a liquid state. The latex was cast and subjected to sulfur curing to result in a unique morphology in the NR composite of a flexible film form. The contents of in situ silica filling were controlled up to 35 parts per one hundred rubber by weight. The silica was locally dispersed around rubber particles to give a filler network. This characteristic morphology brought about the composite of good dynamic mechanical properties. Synchrotron X‐ray absorption near‐edge structure spectroscopy suggested that the sulfidic linkages of the sulfur cross‐linked composites were polysulfidic, S_x (x ≥ 2), and a fraction of shorter polysulfidic linkages became larger with the increase of in situ silica. The present observations will be of use for developing a novel in situ silica‐filled NR composite prepared in NR latex via liquid‐phase soft processing. Copyright © 2011 John Wiley & Sons, Ltd.     

复合材料柔软性对倒金字塔微结构阵列传感器性能的影响

采用模压成型方法制备了2种柔软性不同的热塑性聚氨酯/短切碳纤维/碳纳米管(TPU/SCF-CNT)复合材料复制物, 其表面上具有倒金字塔微结构阵列, 内部有SCF与CNT共同构成的导电通路. 将复合材料复制物和相应的复合材料平整片封装成柔性传感器. 结果表明, 压力作用下传感器内复制物和平整片之间的接触电阻因倒金字塔底棱的形变而显著降低. 对使用柔软性较高的复合材料封装的传感器, 虽然其相对迟滞稍大, 但压力作用下倒金字塔底棱形变量较大, 且复制物和平整片内导电通路增加量较大, 因此其在0~2.5 kPa的线性区内具有较高的灵敏度(0.32 kPa^?1). 制备的2种传感器均具有快速响应特性, 且能在500 s(约1580次)的循环压缩/释放测试(峰值压力约3 kPa)中保持较稳定的电阻响应. 研究表明, 利用模压成型的表面倒金字塔结构复合材料复制物封装成的柔性压力传感器具有良好的传感性能.     

一种高透明、可拉伸导电水凝胶的制备及其在电容传感器中的应用

导电水凝胶由于具备良好的电学特性、可调节的机械性能、易于加工性和生物相容性等,是制备柔性电子设备的理想基材。本文使用马来酸与丙烯酰胺作为共聚单体,氯化锂作为导电离子,N,N'-二甲基双丙烯酰胺作为交联剂,使用光引发剂,采用原位光聚合的方式制备了一种导电水凝胶。制得的水凝胶可见光透过率高达93%,最大拉伸形变~380%,导电率最大为12 S/m。鉴于其优异的综合性能,实验中使用导电水凝胶制备了电容传感器并应用于人体活动监测。结果表明,制备的导电水凝胶电容传感器对不同程度的手指弯曲形变和不同力度的手指触碰均表现出灵敏的响应行为,为未来可穿戴柔性电子产品的发展起到了一定的推动作用。     

Polyaniline‐tailored electromechanical responses of the silver/epoxy conductive adhesive composites

In this article, the electromechanical properties of silver‐in‐epoxy conductive adhesives with the polyaniline (PANI) micron particles as cofillers have been investigated. PANI is a conductive polymer and has a moderate conductivity in between those of silver and epoxy. It was found that PANI can be used to tailor both the adhesive's electrical contact resistance and its relaxation behavior; however, the effects of adding PANI were complex. The addition of small amount of PANI (2 wt %) dramatically increased the contact resistance; it might block the electrical contacts among silver flakes and was not able to form a continuous path among themselves. The addition of more PANI showed a moderate increase in contact resistance, which increased with the weight fraction of PANI from 6 to 15 wt %. Interdependent behavior of compressive strain and relaxation in electrical contact resistance is characterized to evaluate the origin of this relaxation. The addition of PANI made the relaxation in electrical contact resistance more sensitive to the compressive strain and the electromechanical coupling to deviate from the linear relationship. These research findings provide insights into the way to use PANI to tailor the electromechanical properties of the adhesive bonds or joints in the development of advanced functional devices. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013, 51, 1448–1455     

Low percolation conductive graphite flakes-filled poly(urethane-imide) composites with high thermal stability via imidization self-foaming structure

In the study, the conductive graphite flakes filled poly(urethane-imide) composites (PUI/GFs) with high performance were constructed by the thermal imidization self-foaming reaction. It was found that the foaming action could promote the redistribution of GFs during curing process and the formation of stable linear conductive pathways. The percolation threshold of PUI/GFs composites was lowered from 1.26 wt% (2000 mesh GFs) or 0.86 wt% (1000 mesh GFs) to 0.79 wt% (500 mesh GFs), which were relatively low percolation thresholds for polymer/GFs composites so far. When the content of 500 mesh GFs was 4.0 wt%, the electrical conductivity of the composite was as high as 3.96 × 10^?1 S/m. Also, a poly(urethane-imide) (PUI) matrix with excellent thermal stability (T_d10%: 334.97 °C) and mechanical properties (elongation at break: 324.52%, tensile strength: 15.88 MPa) was obtained by introducing the rigid aromatic heterocycle into the polyurethane (PU) hard segments. Moreover, the zero temperature coefficient of resistivity for the composites was observed at the temperature range from 30 °C to 200 °C. Consequently, PUI/GFs composites may provide the novel strategy for considerable conductive materials with high thermal stability in electrical conductivity.     

Synergistic effect of double percolated co‐supportive MWCNT‐CB conductive network for high‐performance EMI shielding application

The recent development in telecommunication technology has led electromagnetic interference (EMI) to a serious threat to both electronic devices and living beings. In this work, we designed a highly efficient EMI shielding material by taking advantage of both carbonaceous hybrid filler and double percolation phenomenon. Here, a flexible, lightweight microwave absorbing conductive polymer composite was fabricated by employing poly (ethylene‐co‐methyl acrylate) and ethylene octene copolymer (EMA/EOC) binary blend as the matrix and multiwall carbon nanotube carbon black (MWCNT/CB) hybrid filler as the conductive moiety. We investigated the effect of MWCNT content in the hybrid composite on mechanical, thermomechanical, electrical, and shielding efficiency. A total EMI shielding efficiency of ?37.4 dB in the X band region was attained with 20 wt% hybrid filler containing 50 wt% MWCNT along with promising mechanical properties.     

Polyion Detection via All‐solid‐contact Paper‐based Polyion‐sensitive Polymeric Membrane Electrodes

The first all‐solid‐contact paper‐based single‐use polyion‐sensitive ion‐selective electrodes (ISEs) are described. These polyion‐sensitive ISEs are fabricated using cellulose filter paper coated with a carbon ink conductive layer. A polyanion sensing membrane is cast on a section of the coated paper and the sensor is insulated, resulting in a disposable, single‐use device. Various polyanions are shown to yield large negative potentiometric responses when using these disposable devices for direct polyanion detection. These new sensors are further demonstrated to be useful in indirect polycation detection when polycations (i. e., polyquaterniums (PQs)) are titrated with polyanionic dextran sulfate (DS). Titrations monitored using these paper‐based, all‐solid‐contact devices yield endpoints proportional to the given PQ concentration present in the test sample.     

Rapid electrothermal response and excellent flame retardancy of ethylene‐vinyl acetate electrothermal film

In this study, high electrical conductivity and flame retardant electrothermal ethylene‐vinyl acetate (EVA) films were fabricated by using carbon nanotubes‐wrapped ammonium polyphosphate (CAPP) and conductive carbon black (CCB). CAPP was used as a synergistic conductive filler and flame retardant to improve the electrical conductivity and fire safety of the electrothermal film at the same time. Besides, the heat release rate (HRR) and the total heat release (THR) of EVA‐5 decreased about 81.5% and 57.3% compared with those of pure EVA film, respectively. Moreover, by incorporating a small amount of CAPP, EVA‐5 can reach up to V‐0 rating with an limiting oxygen index (LOI) value of 31%. EVA film fabricated by CCB and CAPP as conductive material exhibited almost 10 times increment on electrical conductivity than that of same content for CCB alone. And time vs temperature profiles of EVA‐5 showed a stable trend over 3600 seconds without any offset at a given applied voltage of 15 V. Moreover, its excellent cycle heating performance indicated that the electrothermal film can be recycled, which meets the requirements of sustainable development. In a word, this novel strategy provides a simple and effective way to obtain a high conductive and fire safety electrothermal film.