Facile and Large-scale Fabrication of Self-crimping Elastic Fibers for Large Strain Sensors

Stretchable conductive fibers offer unparalleled advantages in the development of wearable strain sensors for smart textiles due to their excellent flexibility and weaveability.However,the practical applications of these fibers in wearable devices are hindered by either contradictory properties of conductive fibers(high stretchability versus high sensing stability),or lack of manufacturing scalability.Herein,we present a facile approach for highly stretchable self-crimping fiber strain sensors based on a polyether-ester(TPEE)elastomer matrix using a side-by-side bicomponent melt-spinning process involving two parallel but attached components with different shrinkage properties.The TPEE component serves as a highly elastic mechanical support layer within the bicomponent fibers,while the conductive component(E-TPEE)of carbon black(CB),multiwalled carbon nanotubes(MWCNTs)and TPEE works as a strain-sensitive layer.In addition to the intrinsic elasticity of the matrix,the TPEE/E-TPEE bicomponent fibers present an excellent form of elasticity due to self-crimping.The self-crimping elongation of the fibers can provide a large deformation,and after the crimp disappears,the intrinsic elastic deformation is responsible for monitoring the strain sensing.The reliable strain sensing range of the TPEE/E-TPEE composite fibers was 160％-270％and could be regulated by adjusting the crimp structure.More importantly,the TPEE/E-TPEE fibers had a diameter of 30-40 μm and tenacity of 40-50 MPa,showing the necessary practicality.This work introduces new possibilities for fiber strain sensors produced in standard industrial spinning machines.     

An Ultrasensitive,Durable and Stretchable Strain Sensor with Crack-wrinkle Structure for Human Motion Monitoring

Flexible strain sensor has promising features in successful application of health monitoring, electronic skins and smart robotics, etc.Here, we report an ultrasensitive strain sensor with a novel crack-wrinkle structure(CWS) based on graphite nanoplates(GNPs)/thermoplastic urethane(TPU)/polydimethylsiloxane(PDMS) nanocomposite. The CWS is constructed by pressing and dragging GNP layer on TPU substrate,followed by encapsulating with PDMS as a protective layer. On the basis of the area statistics, the ratio of the crack and wrinkle structures accounts for 31.8% and 9.5%, respectively. When the sensor is stretched, the cracks fracture, the wrinkles could reduce the unrecoverable destruction of cracks, resulting in an excellent recoverability and stability. Based on introduction of the designed CWS in the sensor, the hysteresis effect is limited effectively. The CWS sensor possesses a satisfactory sensitivity(GF=750 under 24% strain), an ultralow detectable limit(strain=0.1%) and a short respond time of 90 ms. For the sensing service behaviors, the CWS sensor exhibits an ultrahigh durability(high stability>2×10⁴ stretching-releasing cycles). The excellent practicality of CWS sensor is demonstrated through various human motion tests,including vigorous exercises of various joint bending, and subtle motions of phonation, facial movements and wrist pulse. The present CWS sensor shows great developing potential in the field of cost-effective, portable and high-performance electronic skins.     

Resistive gas sensors based on the composites of nanostructured carbonized polyaniline and Nafion

Due to constant necessity to have reliable and sensitive gas sensors in many contemporary technologies, there is a permanent need for development of new sensing platforms with good sensing properties. Here, we demonstrate a novel type of resistive gas sensors based on carbonized polyaniline/Nafion composites. The sensing mechanism of such sensors is based on the sorption of gases by the composites which induce Nafion swelling and decreasing of conductivity. Chemosensitive properties can be tuned by the (i) choice of carbon materials with different conductivities, (ii) Nafion content in the composite, and (iii) thickness of the composite layer. We have shown that the sensors respond to water, acetone, ethanol, and methanol vapors. For the last two cases, we have achieved high sensitivity, fast response, wide concentration range, and good recovery. The use of simultaneous two- and four-point techniques for these sensors provides an internal control of the sensor integrity.     

Thin and high conductive multi-walled carbon nanotubes/polydimethylsiloxane composite film prepared via solvent method as strain sensors

Flexible strain sensors based on conductive fillers and flexible polymers possessed significant advantages in human motion detection. Preparing a strain sensing layer with high electrical conductivity and excellent mechanical property under high content of conductive filler contributed to the stability of flexible strain sensors. In this study, MWCNTs/PDMS composite film was prepared by the organic solvent method. The microstructure, electrical conductivity, mechanical property, and piezoresistive characteristics of the composite film at different MWCNTs contents were characterized and discussed. When the mass fraction of MWCNTs in the composite film was 5%, the composite film exhibited a high electrical conductivity of 9.56 S/m while maintaining ideal mechanical properties, and the film thickness was just about 180 μm. The relationship between electrical signals and film strain was performed. The piezoresistive characteristic results demonstrated that the prepared composite film could be used as flexible strain sensor for human motion detection. The prepared thin MWCNTs/PDMS composite film in this paper illustrated high conductive and desired flexibility, and was an alternative material for human motion detection.     

Natural polymers-enhanced double-network hydrogel as wearable flexible sensor with high mechanical strength and strain sensitivity

Conductive hydrogels have shown great prospects as wearable flexible sensors. Nevertheless, it is still a challenge to construct hydrogel-based sensor with great mechanical strength and high strain sensitivity. Herein, an ion-conducting hydrogel was fabricated by introducing gelatin-dialdehyde β-cyclodextrin (Gel-DACD) into polyvinyl alcohol-borax (PVA-borax) hydrogel network. Natural Gel-DACD network acted as mechanical deformation force through non-covalent cross-linking to endow the polyvinyl alcohol-borax/gelatin-dialdehyde β-cyclodextrin hydrogel (PGBCDH) with excellent mechanical stress (1.35 MPa), stretchability (400%), toughness (1.84 MJ/m³) and great fatigue resistance (200% strain for 100 cycles). Surprisingly, PGBCDH displayed good conductivity of 0.31 S/m after adding DACD to hydrogel network. As sensor, it showed rapid response (168 ms), high strain sensitivity (gage factor (GF) = 8.57 in the strain range of 200%-250%) and reliable sensing stability (100% strain for 200 cycles). Importantly, PGBCDH-based sensor can accurately monitor complex body movements (knee, elbow, wrist and finger joints) and large-scale subtle movements (speech, swallow, breath and facial expressions). Thus, PGBCDH shows great potential for human monitoring with high precision.     

大范围高灵敏度纳米尺度氨气传感器的制备

介绍了基于碳纳米管与聚苯胺纳米纤维的两种氨气传感器的制备与测试,综合运用两种传感器,兼顾了高灵敏度和大范围测量两项互相制约的要求.使用近场电纺技术制备单根聚苯胺纳米纤维传感器,对1×10-6氨气灵敏度达到2.7％,比较了聚苯胺纳米纤维结构和薄膜结构的响应特性.纳米纤维的立体结构可提升传感器性能.使用双向电泳技术制备碳纳米管传感器,对浓度大于20× 10-6 (V/V)的氨气有良好的线性响应.分析了主要功能材料的微结构,阐述了制备技术,比较了响应特性,分析了纤维中气体三维扩散模型,通过计算和测试值,表明响应时间与纤维直径存在反相关性.     

Flexible NH3 sensors fabricated by in situ self-assembly of polypyrrole

Novel flexible NH₃ gas sensors were formed by the in situ self-assembly of polypyrrole (PPy) on plastic substrates. A negatively charged substrate was prepared by the formation of an organic monolayer (3-mercapto-1-propanesulfonic acid sodium salt—MPS) on a polyester (PET) substrate using a pair of comb-like Au electrodes. Two-cycle poly(4-styrenesulfonic acid) sodium salt/poly(allylamine hydrochloride) (PSS/PAH) bilayers (precursor layer) were then layer-by-layer (LBL) deposited on an MPS-modified substrate. Finally, a monolayer of PPy self-assembled in situ and PPy multilayer thin films self-assembled LBL in situ on a (PSS/PAH)₂/MPS/Au/Cr/PET substrate. The thin films were analyzed by atomic force microscopy (AFM). The effects of the precursor layer (PSS), the deposition time of the monolayer of PPy and the number of PPy multilayers on the gas sensing properties (response) and the flexibility of the sensors were investigated to optimize the fabrication of the film. Additionally, other sensing properties such as sensing linearity, reproducibility, response and recovery times, as well as cross-sensitivity effects were studied. The flexible NH₃ gas sensor exhibited a strong response that was comparable to or even greater than that of sensors that were fabricated on rigid substrate at room temperature.     

Magnetic-field-assisted assembly of layered double hydroxide/metal porphyrin ultrathin films and their application for glucose sensors

The ordered ultrathin films (UTFs) based on CoFe-LDH (layered double hydroxide) nanoplatelets and manganese porphyrin (Mn-TPPS) have been fabricated on ITO substrates via a magnetic-field-assisted (MFA) layer-by-layer (LBL) method and were demonstrated as an electrochemical sensor for glucose. The XRD pattern for the film indicates a long-range stacking order in the normal direction of the substrate. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images of the MFA LDH/Mn-TPPS UTFs reveal a continuous and uniform surface morphology. Cyclic voltammetry, impedance spectroscopy, and chronoamperometry were used to evaluate the electrochemical performance of the film, and the results show that the MFA-0.5 (0.5 T magnetic field) CoFe-LDH/Mn-TPPS-modified electrode displays the strongest redox current peaks and fastest electron transfer process compared with those of MFA-0 (without magnetic-field) and MFA-0.15 (0.15 T magnetic field). Furthermore, the MFA-0.5 CoFe-LDH/Mn-TPPS exhibits remarkable electrocatalytic activity toward the oxidation of glucose with a linear response range (0.1-15 mM; R(2) = 0.999), low detection limit (0.79 μM) and high sensitivity (66.3 μA mM(-1) cm(-2)). In addition, the glucose sensor prepared by the MFA LBL method also shows good selectivity and reproducibility as well as resistance to poisoning in a chloride ion solution. Therefore, the novel strategy in this work creates new opportunities for the fabrication of nonenzyme sensors with prospective applications in practical detection.     

Laser-ablated violet phosphorus/graphene heterojunction as ultrasensitive ppb-level room-temperature NO sensor

Two dimensional(2D) materials are promising gas sensing materials, but the most of them need to be heated to show promising sensing performance. Sensing structures with high sensing performance at room-temperature are urgent. Here, another 2D material, violet phosphorus(VP) nanoflake is investigated as gas sensing material. The VP nanoflakes have been effectively ablated to have layers of 1–5 layers by laser ablation in glycol. The VP nanoflakes are combined with graphene to form VP/G heterostru...     

桥连氧化钨纳米线的可控合成及气敏性质

The rapid development of industrialization has resulted in severe environmental problems. A comprehensive assessment of air quality is urgently required all around the world. Among various technologies used in gas molecule detection, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, mass spectroscopy (MS), electrochemical sensors, and metal oxide semiconductor (MOS) gas sensors, MOS gas sensors possess the advantages of small dimension, low power consumption, high sensitivity, low production cost, and excellent silicon chip compatibility. MOS sensors hold great promise for future Internet of Things (IoT) sensors, which will have a profound impact on indoor and outdoor air quality monitoring. The development of nanotechnology has significantly enhanced the development of MOS gas sensors. Among various nanostructures like nanoparticles, nanosheets and nanowires, the emergence of quasi-one-dimensional (q1D) nanowires/nanorods/nanofibers, with unique q1D geometry (facilitating fast carrier transport) and large surface-to-volume ratio, potentially act as ideal sensing channels for MOS sensors with extremely small dimension, and good stability and sensitivity. These structures have thus been the focus of extensive research. Among the various MOS nanomaterials available, tungsten oxide (WO_3-x, 0 ≤ x < 1) nanowires feature the characteristic properties (multiple oxidation states, rich substoichiometric oxides with distinct properties, photo/electrochromism, (photo)catalytic properties, etc.), and unique q1D geometry (single-crystalline pathway for fast carrier transport, large surface-to-volume ratio, etc.). WO_3-x nanowires have broad applications in smart windows, energy conversation & storage, and gas sensing devices, and have thus become a focus of attention. In this paper, the fundamental properties of tungsten oxide, synthesis methods and growth mechanism of tungsten oxide nanowires are reviewed. Among various (vapor-liquid-solid (VLS), vapor-solid (VS) and thermal oxidation) growth methods, the thermal oxidation method enables an in situ integration of WO_3-x nanowires on predefined electrodes (so-called bridged nanowire devices) via the oxidation of lithographically patterned W film at relatively low growth temperature (~500 ℃) because of interfacial strain, defects and oxygen on the surface of the W film. The novel bridged nanowire-based sensor devices outperform traditional lateral nanowire devices in terms of larger exposure area, low power consumption via self-heating, and greater convenience in device processing. Recent progress in bridged WO_3-x nanowire devices and sensitive NO_x molecule detection under low power consumption have also been reviewed. Power consumption of as low as a few milliwatts was achieved, and the detection limit of NO₂ was reduced to 0.3 ppb (1 ppb = 1 × 10^-9, volume fraction). In situ formed bridged WO_3-x nanowire devices potentially satisfy the strict requirements of IoT sensors (small dimension, low power consumption, high integration, low cost, high sensitivity, and selectivity), and hold great promises for future IoT sensors.     

Versatile fullerenes as sensor materials

The last century outstanding discovery of fullerenes (or C₆₀), as they are popularly called ‘buckyball’ structured molecules with icosahedral spherical structure, consists of 60 sp^2-hybridized carbon atoms. These fullerenes have created immense applications in various fields, such as catalysts, sensors, photocatalysts, energy production, and storage materials. Fullerenes because of their improved conductivity, charge transfer, and photophysical properties have gained considerable attention, particularly in sensor area. The activity of sensors depends upon the interactions between fullerene and the sensing material. Among all the types of fullerenes, C₆₀ has been extensively used. This review is an attempt to cover different aspects of fullerene-based sensing devices, wherein fullerenes act as important component (s) of the sensor device because of their electron-accepting properties. We will discuss the fullerene-based sensors for diverse applications as strain/gas sensors, electrochemical sensors, and optical sensors as much effort has been recently made to detect different analytes such as gases, volatile organic compounds, metal ions, anions, and biomolecules.     

MXene-composited highly stretchable,sensitive and durable hydrogel for flexible strain sensors

The flourishing development in flexible electronics has provoked intensive research in flexible strain sensors to realize accurate perception acquisition under different external stimuli.However,building hydrogel-based strain sensors with high stretchability and sensitivity remains a great challenge.Herein,MXene nanosheets were composited into polyacrylamide-sodium alginate matrix to construct mechanical robust and sensitive double networked hydrogel strain sensor.The hydrophilic MXene nanosheets formed strong interactions with the polymer matrix and endowed the hydrogel with excellent tensile properties(3150%),compliant mechanical strength(2.03 kPa~(-1) in Young's Module) and long-lasting stability and fatigue resistance(1000 dynamic cycles under 1,600% strain).Due to the highly oriented MXene-based three dimensional conductive networks,the hydrogel sensor achieved extremely high tensile sensitivity(18.15 in gauge factor) and compression sensitivity(0.38 kPa~(-1) below 3 kPa).MXene hydrogel-based strain sensors also displayed negligible hysteresis in electromechanical performance,typical frequent-independent feature and rapid response time to external stimuli.Moreover,the sensor exhibited accurate response to different scales of human movements,providing potential application in speech recognition,expression recognition and handwriting verification.     

Optical sensors with molecularly imprinted nanospheres: a promising approach for robust and label-free detection of small molecules

Molecularly imprinted nanospheres obtained by miniemulsion polymerization have been applied as the sensitive layer for label-free direct optical sensing of small molecules. Using these particles as the sensitive layer allowed for improving response times in comparison to sensors using MIP layers. As a model compound, well-characterized nanospheres imprinted against l-Boc-phenylalanine anilide (l-BFA) were chosen. For immobilization, a simple concept based on electrostatic adsorption was used, showing its applicability to different types of surfaces, leading to a good surface coverage. The sensor showed short response times, good selectivity, and high reversibility with a limit of detection down to 60 μM and a limit of quantitation of 94 μM. Furthermore, reproducibility, selectivity, and long-term stability of the sensitive layers were tested. The best results were achieved with an adsorption on aminopropylsilane layers, showing a chip-to-chip reproducibility of 22%. Furthermore, the sensors showed no loss in signal after a storage time of 1 year.     

Highly improved carbon dioxide sensitivity and selectivity of black phosphorene sensor by vacancy doping: A quantum chemical perspective

The adsorption and sensing properties of a carbon dioxide (CO₂) molecule on the pristine (BP) and vacancy-doped (DP) black phosphorusmono layers have been investigated using the periodic density functional theory at Heyd-Scuseria-Ernzerhof (HSE06)/triple-zeta valence polarization (TZVP). For both sensors, the most stable structures among the recognized possibilities preferred a linear configuration for carbon dioxide, with a shorter equilibrium distance (2.13 Å) on the defect-containing surface. Although carbon dioxide was weakly physiosorbed on both phosphorene sensors (up to −2.52 kcal/mol), the defect-engineered material presented highly improved sensitivity (by a factor of 6.6) to CO₂ compared to the pristine layer. The former was also a (2.6 times) better work function sensor of carbon dioxide. At the same time, recovery was extremely fast (lasting for 70 ps at most) at room temperature. The selectivity coefficient of carbon dioxide was also strikingly high (64.0). The improved nanosensor would be a step forward in the rational design of highly sensitive and reusable detectors of carbon dioxide.     

纳米In_2O_3催化发光传感器快速检测三氯乙烯

本文以纳米In_2O_3为传感元件,设计构建了快速检测三氯乙烯的催化发光传感器。该传感器对三氯乙烯具有灵敏度高、特异性好及响应快速等优点。在检测波长为440nm,工作温度为250℃条件下,催化发光信号强度与三氯乙烯浓度呈良好的线性关系,其线性范围为20~1 200mg/m~3(r=0.9984),检出限(S/N=3)为8.0mg/m~3。苯、甲苯、邻二甲苯、对二甲苯、间二甲苯、氨水、甲醇、乙醇、甲醛、乙醛、四氯化碳、甲酸、乙酸、乙酸乙酯、正己烷及环己烷经过此传感器时,只有乙醇产生弱的发光信号,其它物质不产生响应信号。在72h内24次测定100mg/m~3的三氯乙烯,所得相对标准偏差小于5.0%,表明传感器稳定性好,使用寿命长。将此传感器用于三氯乙烯的分析,加标回收率为93.2%~103%。     

High-Performance Sensor Based on Thin-Film Metallic Glass/Ultra-nanocrystalline Diamond/ZnO Nanorod Heterostructures for Detection of Hydrogen Gas at Room Temperature

This article outlines a novel material to enable the detection of hydrogen gas. The material combines thin-film metallic glass (TFMG), ultra-nanocrystalline diamond (UNCD), and ZnO nanorods (ZNRs) and can be used as a device for effective hydrogen gas sensing. Three sensors were fabricated by using combinations of pure ZNRs (Z), UNCD/ZNRs (DZ), and TFMG/UNCD/ZNRs (MDZ). The MDZ device exhibited a performance superior to the other configurations, with a sensing response of 34 % under very low hydrogen gas concentrations (10 ppm) at room temperature. Remarkably, the MDZ-based sensor exhibits an ultra-high sensitivity of 60.5 % under 500 ppm H₂. The MDZ sensor proved very fast in terms of response time (20 s) and recovery time (35 s). In terms of selectivity, the sensors were particularly suited to hydrogen gas. The sensor achieved the same response performance even after two months, thereby demonstrating the superior stability. It is postulated that the superior performance of MDZ can be attributed to defect-related adsorption as well as charge carrier density. This paper also discusses the respective energy band models of these heterostructures and also the interface effect on the gas sensing enhancements. The results indicate that the proposed hybrid TFMG/UNCD/ZNRs nanostructures could be utilized as high-performance hydrogen gas sensors.     

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3(PTP/WO3)organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction(XRD),transmission electron microscopy(TEM)and thermo-gravimetric analysis(TGA).The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.     

基于低温等离子体辅助催化发光的乙烯传感器

将等离子体的高活化性能与催化发光的传感特性相结合,以成本低、合成简单的碱土金属纳米MgO为传感材料,构建了基于低温等离子体辅助的催化发光传感器,用于乙烯的快速检测.由于等离子体具有高活化性能,本方法的检测温度远低于传统的催化发光检测法的常用温度(300~500℃),无需加热装置,在室温下实现了对乙烯快速、灵敏的检测.室温(25℃)下,对乙烯的检出限为37 ng/mL (30 ppm),线性范围为112~4997 ng/mL (90~3998 ppm, R=0.97669),传感器具有良好的选择性和重现性.此传感器制备简单、稳定性高、低能耗、成本低,与传统的气体检测方法相比具有良好的实用性和普适性,为开发性能优异的新型催化发光传感器提供了策略.     

Preparation of polyelectrolyte multilayer membranes by dynamic layer-by-layer process for pervaporation separation of alcohol/water mixtures

In the past decades, the layer-by-layer (LBL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes. However, to obtain a good separation capability, LBL adsorption involved relatively long periods because 50–60 bilayers were normally required. The aim of this study was to develop such a new method that would allow simplification of the LBL procedure. LBL adsorption was proposed to proceed under a dynamic condition to prepare polyelectrolyte multilayer membranes. The polyacrylic acid (PAA) and polyethyleneimine (PEI) were alternatively deposited on polyethersulfone (PES) ultrafiltration support membrane under a pressure of 0.1 MPa. The polyelectrolyte multilayer membranes prepared by dynamic LBL process were compared with those prepared by the static LBL process for the pervaporation separation of water–ethanol mixture. The results suggested that a relatively high separation factor could be obtained with only four composite bilayers by using dynamic LBL process. The preparative conditions including bilayer number, filtration time of the first PAA layer, reaction time, ratio between polayanion and polycation concentrations, PAA molecular weight and salt addition were investigated. The pervaporation conditions such as feed temperature and water concentration in the feed were also evaluated. Under the temperature of 40 °C, the separation factor and the permeate flux of the polyelectrolyte multilayer membranes were about 1207 and 140 g/(m² h), respectively.     

Sensor integration in rubber gaskets for structural health monitoring made by compression molding

This research work shows the integration process and characterization of a miniaturized strain gauge sensor in rubber O-rings for structural health monitoring (SHM). Strain gauges have been successfully embedded during compression molding, which is a commonly used fabrication method of rubber components. The sensor signal is correlated with the contact pressure of the gasket that abates over time due to aging processes. This can be exploited for lifetime prediction. Embedding sensors into rubber applying compression molding is a novel method that allows the integration into non-liquid elastomers. The strain gauge resistance correlates linearly to the contact pressure. An artificial aging test exhibits an exponential decrease in the resistance caused by the relaxation processes during the accelerated aging of the elastomer at 70 °C for 72 h. Uniaxial tensile testing with dumbbell specimens reveals the influence of the integrated sensors. It is demonstrated that the influence heavily depends on the sensor size.