Improvement of the Piezoresistive Behavior of Poly (vinylidene fluoride)/Carbon Nanotube Composites by the Addition of Inorganic Semiconductor Nanoparticles.

Conductive polymer composites (CPCs), obtained by incorporating conductive fillers into a polymer matrix, are suitable for producing strain sensors for structural health monitoring (SHM) in infrastructure. Here, the effect of the addition of inorganic semiconductor nanoparticles (INPs) to a poly (vinylidene fluoride) (PVDF) composite filled with multi-walled carbon nanotubes (MWCNTs) on the piezoresistive behavior is investigated. INPs with different morphologies and sizes are synthesized by a hydrothermal method. The added inorganic oxide semiconductors showed two distinct morphologies, including different phases. While particles with flower-like plate morphology contain phases of orth-ZnSnO3 and SnO, the cauliflower-like nanoparticles contain these metal oxides and ZnO. The nanoparticles are characterized by field-emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD), and the nanocomposites by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Cyclic tensile testing is applied to determine the strain-sensing behavior of PVDF/1 wt% MWCNT nanocomposites with 0-10 wt% inorganic nanoparticles. Compared to the PVDF/1 wt% MWCNT nanocomposite, the piezoresistive sensitivity is higher after the addition of both types of nanoparticles and increases with their amount. Thereby, nanoparticles with flower-like plate structures improve strain sensing behavior slightly more than nanoparticles with cauliflower-like structures. The thermogravimetric analysis results showed that the morphology of the semiconductor nanoparticles added to the PVDF/MWCNT matrix influences the changes in thermal properties.

Retraction of "Fe3O4 Nanoparticles Grown on Cellulose/GO Hydrogels as Advanced Catalytic Materials for the Heterogeneous Fenton-like Reaction".

[This retracts the article DOI: 10.1021/acsomega.9b00170.].

Carbon Nanotube-Polyurethane Composite Sheets for Flexible Thermoelectric Materials.

Integration of single-wall carbon nanotubes (SWCNTs) in the form of fabriclike sheets or other preformed assemblies (films, fibers, etc.) simplifies their handling and allows for composites with higher nanotube contents, which is needed to better exploit their outstanding properties and achieve multifunctional materials with improved performance. Here, we show the development of p-type SWCNT-thermoplastic polyurethane (TPU) fabric materials with a wide range of SWCNT contents (from 5 to 90 wt %) by employing a one-step filtration method using a suspension of SWCNTs in a TPU solvent/nonsolvent mixture. The mechanical and thermoelectric (TE) properties of these SWCNT-TPU nanocomposites were tailored by varying the SWCNT/TPU wt % ratio, achieving significant advantages relative to the pristine SWCNT buckypaper (BP) sheets in terms of strength and stretchability. In particular, the SWCNT-TPU nanocomposite with a 50/50 wt % ratio composition (equivalent to 15 vol % of SWCNTs) shows a power factor (PF) of 57 µW m-1 K-2, slightly higher compared to the PF of the SWCNT BP prepared under the same conditions (54 µW m-1 K-2), while its mechanical properties significantly increased (e.g., ∼7-, 25-, and 250-fold improvements in stiffness, strength, and tensile toughness, respectively). These results represent a significant step toward the development of easy-to-process self-supporting and stretchable materials with robust mechanical properties for flexible thermoelectric devices.

Change of Conduction Mechanism in Polymer/Single Wall Carbon Nanotube Composites upon Introduction of Ionic Liquids and Their Investigation by Transient Absorption Spectroscopy: Implication for Thermoelectric Applications.

Polymer composites based on polycarbonate (PC) and polyether ether ketone (PEEK) filled with single-walled carbon nanotubes (SWCNTs, 0.5-2.0 wt %) were melt-mixed to investigate their suitability for thermoelectric applications. Both types of polymer composites exhibited positive Seebeck coefficients (S), indicative for p-type thermoelectric materials. As an additive to improve the thermoelectric performance, three different ionic liquids (ILs), specifically THTDPCl, BMIMPF6, and OMIMCl, were added with the aim to change the thermoelectric conduction type of the composites from p-type to n-type. It was found that in both composite types, among the three ILs employed, only the phosphonium-based IL THTDPCl was able to activate the p- to n-type switching. Moreover, it is revealed that for the thermoelectric parameters and performance, the SWCNT:lL ratio plays a role. In the selected systems, S-values between 61.3 µV/K (PEEK/0.75 wt % SWCNT) and -37.1 µV/K (PEEK/0.75 wt % SWCNT + 3 wt % THTDPCl) were reached. In order to shed light on the physical origins of the thermoelectric properties, the PC-based composites were studied using ultrafast laser time-resolved transient absorption spectroscopy (TAS). The TAS studies revealed that the introduction of ILs in the developed PC/CNT composites leads to the formation of biexcitons when compared to the IL-free composites. Moreover, no direct correlation between S and exciton lifetimes was found for the IL-containing composites. Instead, the exciton lifetime decreases while the conductivity seems to increase due to the availability of more free-charge carriers in the polymer matrix.

Thermoelectric Properties of Cotton Fabrics Dip-Coated in Pyrolytically Stripped Pyrograf® III Carbon Nanofiber Based Aqueous Inks.

The transport properties of commercial carbon nanofibers (CNFs) produced by chemical vapor deposition (CVD) depend on the various conditions used during their growth and post-growth synthesis, which also affect their derivate CNF-based textile fabrics. Here, the production and thermoelectric (TE) properties of cotton woven fabrics (CWFs) functionalized with aqueous inks made from different amounts of pyrolytically stripped (PS) Pyrograf® III PR 25 PS XT CNFs via dip-coating method are presented. At 30 °C and depending on the CNF content used in the dispersions, the modified textiles show electrical conductivities (σ) varying between ~5 and 23 S m-1 with a constant negative Seebeck coefficient (S) of -1.1 µVK-1. Moreover, unlike the as-received CNFs, the functionalized textiles present an increase in their σ from 30 °C to 100 °C (dσ/dT > 0), explained by the 3D variable range hopping (VRH) model as the charge carriers going beyond an aleatory network of potential wells by thermally activated hopping. However, as it happens with the CNFs, the dip-coated textiles show an increment in their S with temperature (dS/dT > 0) successfully fitted with the model proposed for some doped multiwall carbon nanotube (MWCNT) mats. All these results are presented with the aim of discerning the authentic function of this type of pyrolytically stripped Pyrograf® III CNFs on the thermoelectric properties of their derived textiles.

Influence of Polyvinylpyrrolidone on Thermoelectric Properties of Melt-Mixed Polymer/Carbon Nanotube Composites.

For thermoelectric applications, both p- and n-type semi-conductive materials are combined. In melt-mixed composites based on thermoplastic polymers and carbon nanotubes, usually the p-type with a positive Seebeck coefficient (S) is present. One way to produce composites with a negative Seebeck coefficient is to add further additives. In the present study, for the first time, the combination of single-walled carbon nanotubes (SWCNTs) with polyvinylpyrrolidone (PVP) in melt-mixed composites is investigated. Polycarbonate (PC), poly(butylene terephthalate) (PBT), and poly(ether ether ketone) (PEEK) filled with SWCNTs and PVP were melt-mixed in small scales and thermoelectric properties of compression moulded plates were studied. It could be shown that a switch in the S-value from positive to negative values was only possible for PC composites. The addition of 5 wt% PVP shifted the S-value from 37.8 µV/K to -31.5 µV/K (2 wt% SWCNT). For PBT as a matrix, a decrease in the Seebeck coefficient from 59.4 µV/K to 8.0 µV/K (8 wt% PVP, 2 wt% SWCNT) could be found. In PEEK-based composites, the S-value increased slightly with the PVP content from 48.0 µV/K up to 54.3 µV/K (3 wt% PVP, 1 wt% SWCNT). In addition, the long-term stability of the composites was studied. Unfortunately, the achieved properties were not stable over a storage time of 6 or 18 months. Thus, in summary, PVP is not suitable for producing long-term stable, melt-mixed n-type SWCNT composites.

Thermoelectric Properties of N-Type Poly (Ether Ether Ketone)/Carbon Nanofiber Melt-Processed Composites.

The thermoelectric properties, at temperatures from 30 °C to 100 °C, of melt-processed poly(ether ether ketone) (PEEK) composites prepared with 10 wt.% of carbon nanofibers (CNFs) are discussed in this work. At 30 °C, the PEEK/CNF composites show an electrical conductivity (σ) of ~27 S m-1 and a Seebeck coefficient (S) of -3.4 µV K-1, which means that their majority charge carriers are electrons. The origin of this negative Seebeck is deduced because of the impurities present in the as-received CNFs, which may cause sharply varying and localized states at approximately 0.086 eV above the Fermi energy level (EF) of CNFs. Moreover, the lower S, in absolute value, found in PEEK/CNF composites, when compared with the S of as-received CNFs (-5.3 µV K-1), is attributed to a slight electron withdrawing from the external layers of CNFs by the PEEK matrix. At temperatures from 30 °C to 100 °C, the σ (T) of PEEK/CNF composites, in contrast to the σ (T) of as-received CNFs, shows a negative temperature effect, understood through the 3D variable-range hopping (VRH) model, as a thermally activated hopping mechanism across a random network of potential wells. Moreover, their nonlinear S (T) follows the same behavior reported before for polypropylene composites melt-processed with similar CNFs at the same interval of temperatures.

Polyethylene Glycol as Additive to Achieve N-Conductive Melt-Mixed Polymer/Carbon Nanotube Composites for Thermoelectric Application.

The development of thermoelectric (TE) materials based on thermoplastic polymers and carbon nanotubes is a focus of current TE research activities. For a TE module, both p- and n-conductive composites are required, whereby the production of n-conductive materials is a particular challenge. The present study investigates whether adding polyethylene glycol (PEG) as n-dopant during the melt-mixing of the conductive composites based on polycarbonate, poly(ether ether ketone), or poly(butylene terephthalate) with singlewalled carbon nanotubes (0.5 to 2 wt%) is a possible solution. It was shown that for all three polymer types, a change in the sign of the Seebeck coefficient from positive to negative could be achieved when at least 1.5 wt% PEG was added. The most negative Seebeck coefficients were determined to be -30.1 µV/K (PC), -44.1 µV/K (PEEK), and -14.5 µV/K (PBT). The maximal power factors ranged between 0.0078 µW/m·K2 (PC), 0.035 µW/m·K2 (PEEK), and 0.0051 µW/m·K2 (PBT).

CuxCo1-xFe2O4 (x = 0.33, 0.67, 1) Spinel Ferrite Nanoparticles Based Thermoplastic Polyurethane Nanocomposites with Reduced Graphene Oxide for Highly Efficient Electromagnetic Interference Shielding.

CuxCo1-xFe2O4 (x = 0.33, 0.67, 1)-reduced graphene oxide (rGO)-thermoplastic polyurethane (TPU) nanocomposites exhibiting highly efficient electromagnetic interference (EMI) shielding were prepared by a melt-mixing approach using a microcompounder. Spinel ferrite Cu0.33Co0.67Fe2O4 (CuCoF1), Cu0.67Co0.33Fe2O4 (CuCoF2) and CuFe2O4 (CuF3) nanoparticles were synthesized using the sonochemical method. The CuCoF1 and CuCoF2 exhibited typical ferromagnetic features, whereas CuF3 displayed superparamagnetic characteristics. The maximum value of EMI total shielding effectiveness (SET) was noticed to be 42.9 dB, 46.2 dB, and 58.8 dB for CuCoF1-rGO-TPU, CuCoF2-rGO-TPU, and CuF3-rGO-TPU nanocomposites, respectively, at a thickness of 1 mm. The highly efficient EMI shielding performance was attributed to the good impedance matching, conductive, dielectric, and magnetic loss. The demonstrated nanocomposites are promising candidates for a lightweight, flexible, and highly efficient EMI shielding material.

Nonlinear Thermopower Behaviour of N-Type Carbon Nanofibres and Their Melt Mixed Polypropylene Composites.

The temperature dependent electrical conductivity σ (T) and thermopower (Seebeck coefficient) S (T) from 303.15 K (30 °C) to 373.15 K (100 °C) of an as-received commercial n-type vapour grown carbon nanofibre (CNF) powder and its melt-mixed polypropylene (PP) composite with 5 wt.% of CNFs have been analysed. At 30 °C, the σ and S of the CNF powder are ~136 S m-1 and -5.1 µV K-1, respectively, whereas its PP/CNF composite showed lower conductivities and less negative S-values of ~15 S m-1 and -3.4 µV K-1, respectively. The σ (T) of both samples presents a dσ/dT < 0 character described by the 3D variable range hopping (VRH) model. In contrast, their S (T) shows a dS/dT > 0 character, also observed in some doped multiwall carbon nanotube (MWCNT) mats with nonlinear thermopower behaviour, and explained here from the contribution of impurities in the CNF structure such as oxygen and sulphur, which cause sharply varying and localized states at approximately 0.09 eV above their Fermi energy level (EF).

High-Performance, Lightweight, and Flexible Thermoplastic Polyurethane Nanocomposites with Zn2+-Substituted CoFe2O4 Nanoparticles and Reduced Graphene Oxide as Shielding Materials against Electromagnetic Pollution.

The development of flexible, lightweight, and thin high-performance electromagnetic interference shielding materials is urgently needed for the protection of humans, the environment, and electronic devices against electromagnetic radiation. To achieve this, the spinel ferrite nanoparticles CoFe2O4 (CZ1), Co0.67Zn0.33Fe2O4 (CZ2), and Co0.33Zn0.67Fe2O4 (CZ3) were prepared by the sonochemical synthesis method. Further, these prepared spinel ferrite nanoparticles and reduced graphene oxide (rGO) were embedded in a thermoplastic polyurethane (TPU) matrix. The maximum electromagnetic interference (EMI) total shielding effectiveness (SET) values in the frequency range 8.2-12.4 GHz of these nanocomposites with a thickness of only 0.8 mm were 48.3, 61.8, and 67.8 dB for CZ1-rGO-TPU, CZ2-rGO-TPU, and CZ3-rGO-TPU, respectively. The high-performance electromagnetic interference shielding characteristics of the CZ3-rGO-TPU nanocomposite stem from dipole and interfacial polarization, conduction loss, multiple scattering, eddy current effect, natural resonance, high attenuation constant, and impedance matching. The optimized CZ3-rGO-TPU nanocomposite can be a potential candidate as a lightweight, flexible, thin, and high-performance electromagnetic interference shielding material.

Highly Tunable Piezoresistive Behavior of Carbon Nanotube-Containing Conductive Polymer Blend Composites Prepared from Two Polymers Exhibiting Crystallization-Induced Phase Separation.

Conductive polymer composites (CPCs) are suitable as piezoresistive-sensing materials. When using CPCs for strain sensing, it is still a big challenge to simultaneously improve the piezoresistive sensitivity and linearity along with the electrical conductivity and mechanical properties. Here, highly tunable piezoresistive behavior is reported for multiwalled carbon nanotube (CNT)-filled CPCs based on blends of two semicrystalline polymers poly(vinylidene fluoride) (PVDF) and poly(butylene succinate) (PBS), which are miscible in the melt. When cooling the homogeneous mixture of the blend components, successive crystallization of PVDF and PBS occurs, creating complex crystalline structures in a mixed amorphous phase. The morphology of the blend matrix, the crystallinity of the blend components, and the dispersion and location of the CNTs in the blend depend on the CNT content and the blend composition. Compared with PVDF/CNT composites, the substitution of 10 to 50 wt % PVDF by PBS in the composites shifts the electrical percolation concentration Φc from 0.79 wt % to filler contents as low as 0.50 wt % while improving the stretchability. The piezoresistive behavior is highly tunable by changing the PVDF/PBS ratio. The ternary composites with matrix compositions of PVDF (90 wt %)/PBS (10 wt %) and PVDF (50 wt %)/PBS (50 wt %) show either higher piezoresistive sensitivity or linearity, respectively, caused by the differences in the microstructure of the CPCs. For example, the crystallinity of PBS in the ternary composites increased from 19.8% to 52.0% as the PBS content increased from 10 wt % to 50 wt %, which is connected with altered CNT distribution and conductive network structure and substantial improvement of the linearity of the electrical response to strains up to >20%. Our findings highly contribute to the understanding of the piezoresistive properties of CPCs based on two semicrystalline polymers and are important for future studies to tune the piezoresistive behavior to achieve simultaneously improved sensitivity and linearity.

The Localization Behavior of Different CNTs in PC/SAN Blends Containing a Reactive Component.

Co-continuous blend systems of polycarbonate (PC), poly(styrene-co-acrylonitrile) (SAN), commercial non-functionalized multi-walled carbon nanotubes (MWCNTs) or various types of commercial and laboratory functionalized single-walled carbon nanotubes (SWCNTs), and a reactive component (RC, N-phenylmaleimide styrene maleic anhydride copolymer) were melt compounded in one step in a microcompounder. The blend system is immiscible, while the RC is miscible with SAN and contains maleic anhydride groups that have the potential to reactively couple with functional groups on the surface of the nanotubes. The influence of the RC on the localization of MWCNTs and SWCNTs (0.5 wt.%) was investigated by transmission electron microscopy (TEM) and energy-filtered TEM. In PC/SAN blends without RC, MWCNTs are localized in the PC component. In contrast, in PC/SAN-RC, the MWCNTs localize in the SAN-RC component, depending on the RC concentration. By adjusting the MWCNT/RC ratio, the localization of the MWCNTs can be tuned. The SWCNTs behave differently compared to the MWCNTs in PC/SAN-RC blends and their localization occurs either only in the PC or in both blend components, depending on the type of the SWCNTs. CNT defect concentration and surface functionalities seem to be responsible for the localization differences.

Blend Structure and n-Type Thermoelectric Performance of PA6/SAN and PA6/PMMA Blends Filled with Singlewalled Carbon Nanotubes.

The present study investigates how the formation of melt-mixed immiscible blends based on PA6/SAN and PA6/PMMA filled with single walled nanotubes (SWCNTs) affects the thermoelectric (TE) properties. In addition to the detailed investigation of the blend morphology with compositions between 100/0 wt.% and 50/50 wt.%, the thermoelectric properties are investigated on blends with different SWCNT concentrations (0.25-3.0 wt.%). Both PA6 and the blend composites with the used type of SWCNTs showed negative Seebeck coefficients. It was shown that the PA6 matrix polymer, in which the SWCNTs are localized, mainly influenced the thermoelectric properties of blends with high SWCNT contents. By varying the blend composition, an increase in the absolute Seebeck coefficient, power factor (PF), and figure of merit (ZT) was achieved compared to the PA6 composite which is mainly related to the selective localization and enrichment of SWCNTs in the PA6 matrix at constant SWCNT loading. The maximum PFs achieved were 0.22 µW/m·K2 for PA6/SAN/SWCNT 70/30/3 wt.% and 0.13 µW/m·K2 for PA6/PMMA/SWCNT 60/40/3 wt.% compared to 0.09 µW/m·K2 for PA6/3 wt.% SWCNT which represent increases to 244% and 144%, respectively. At higher PMMA or SAN concentration, the change from matrix-droplet to a co-continuous morphology started, which, despite higher SWCNT enrichment in the PA6 matrix, disturbed the electrical conductivity, resulting in reduced PFs with still increasing Seebeck coefficients. At SWCNT contents between 0.5 and 3 wt.% the increase in the absolute Seebeck coefficient was compensated by lower electrical conductivity resulting in lower PF and ZT as compared to the PA6 composites.

Ultrathin structures derived from interfacially modified polymeric nanocomposites to curb electromagnetic pollution.

The use of electronic devices and wireless networks is increasing rapidly, and electromagnetic (EM) pollution remediation remains a challenge. We employed a unique approach to fabricate two ultrathin (approx. 53 µm) multilayered assemblies to address this. By sequentially stacking thin films of polyvinylidene difluoride (PVDF) and polycarbonate (PC) nanocomposites and interfacially locking them with a mutually miscible polymer (PMMA, polymethyl methacrylate), materials with enhanced structural properties and electromagnetic interference (EMI) shielding performance can be designed. Utilizing reduced graphene oxide (rGO) and molybdenum disulfide (MoS2) as a template, ferrite was grown on the surface to design two different nanohybrid structures (rGO-Fe3O4 and MoS2-Fe3O4). PVDF was composited with either rGO-Fe3O4 or MoS2-Fe3O4, and multiwall carbon nanotubes (CNTs) were dispersed in the PC component. As PC and PVDF are immiscible, their poor interface would result in inferior structural properties, which can be challenging in designing EMI shielding materials due to cyclic thermal fatigue. Hence, PMMA is sandwiched to interfacially stitch the components (PC and PVDF) and improve interfacial adhesion. This was confirmed using SEM/EDS and Raman mapping/imaging. The mechanical stability of the multilayered assemblies was characterized using a dynamic mechanical analyzer (DMA), and the storage modulus was found to be as high as 2767 MPa at 40 °C (@constant frequency and strain amplitude), for the multilayered film with rGO-Fe3O4 in PVDF, PMMA as a sandwich layer and CNTs in PC. A typical assembly of 9 multilayers (∼480 µm) with rGO-Fe3O4 in PVDF, and CNTs in PC, and interfacially stitched with PMMA gave rise to a high EMI shield effectiveness (SET) of -26.3 dB @ 26.5 GHz. This unique arrangement of a multilayered assembly suppressed EMI primarily by absorption.

Effect of Filler Synergy and Cast Film Extrusion Parameters on Extrudability and Direction-Dependent Conductivity of PVDF/Carbon Nanotube/Carbon Black Composites.

In the present study, melt-mixed composites based of poly (vinylidene fluoride) (PVDF) and fillers with different aspect ratios (carbon nanotubes (CNTs), carbon black (CB)) and their mixtures in composites were investigated whereby compression-molded plates were compared with melt-extruded films. The processing-related orientation of CNTs with a high aspect ratio leads to direction-dependent electrical and mechanical properties, which can be reduced by using mixed filler systems with the low aspect ratio CB. An upscaling of melt mixing from small scale to laboratory scale was carried out. From extruded materials, films were prepared down to a thickness of 50 µm by cast film extrusion under variation of the processing parameters. By combining CB and CNTs in PVDF, especially the electrical conductivity through the film could be increased compared to PVDF/CNT composites due to additional contact points in the sample thickness. The alignment of the fillers in the two directions within the films was deduced from the differences in electrical and mechanical film properties, which showed higher values in the extrusion direction than perpendicular to it.

Aerogels Based on Reduced Graphene Oxide/Cellulose Composites: Preparation and Vapour Sensing Abilities.

This paper reports on the preparation of cellulose/reduced graphene oxide (rGO) aerogels for use as chemical vapour sensors. Cellulose/rGO composite aerogels were prepared by dissolving cellulose and dispersing graphene oxide (GO) in aqueous NaOH/urea solution, followed by an in-situ reduction of GO to reduced GO (rGO) and lyophilisation. The vapour sensing properties of cellulose/rGO composite aerogels were investigated by measuring the change in electrical resistance during cyclic exposure to vapours with varying solubility parameters, namely water, methanol, ethanol, acetone, toluene, tetrahydrofuran (THF), and chloroform. The increase in resistance of aerogels on exposure to vapours is in the range of 7 to 40% with methanol giving the highest response. The sensing signal increases almost linearly with the vapour concentration, as tested for methanol. The resistance changes are caused by the destruction of the conductive filler network due to a combination of swelling of the cellulose matrix and adsorption of vapour molecules on the filler surfaces. This combined mechanism leads to an increased sensing response with increasing conductive filler content. Overall, fast reaction, good reproducibility, high sensitivity, and good differentiation ability between different vapours characterize the detection behaviour of the aerogels.

Tuning the Piezoresistive Behavior of Poly(Vinylidene Fluoride)/Carbon Nanotube Composites Using Poly(Methyl Methacrylate).

In conductive polymer composites (CPCs), which can be used as both strain sensors and materials with self-diagnosis capabilities for structural health monitoring, the piezoresistive sensitivity can be tuned by changing the electrical filler network structure, mainly influenced by the conductive filler content. Typically, the electrical resistance increases exponentially with strain, and the piezoresistive sensitivity and linearity cannot be improved simultaneously. In this work, we report a facile method to tune the piezoresistive behavior of melt-mixed poly(vinylidene fluoride) (PVDF)/carbon nanotube (CNT, 0.75-2.0 wt %) composites using blending with poly(methyl methacrylate) (PMMA, 5-30 wt %). PVDF and PMMA are completely miscible in the melt state regardless of the proportion. For PVDF-rich blends, the crystallization of PVDF induces separation of the PVDF crystal region from the miscible PVDF/PMMA amorphous blend part during the cooling process. Addition of PMMA tuned the piezoresistive strain behavior and improved the electrical conductivity and toughness at the same time. The PVDF/PMMA/CNT composites show higher sensitivity at low strains than their PVDF/CNT counterparts with comparable initial resistivity. For example, ΔR/R0 at 5% strain is 18.6% for the PVDF(80)/PMMA(20) blend containing 0.75 wt % CNT versus 11.0% for PVDF containing 1 wt % CNT, both having a volume resistivity of around 104 Ω·cm. The PVDF/PMMA/CNT blend composites also show a less steep exponential increase in the sensing response at higher strains, indicating better linearity. These differences are due to the altered microstructure of the composites and the more homogeneous distribution of CNTs between the smaller and less numerous PVDF crystallites when PMMA is added. The concept of modifying the composite microstructure by adding another commercially available miscible polymer offers a simple and effective way to tune the piezoresistive behavior and improve mechanical properties of CPC sensor materials.

Tuning the Structure and Performance of Bulk and Porous Vapor Sensors Based on Co-continuous Carbon Nanotube-Filled Blends of Poly(vinylidene fluoride) and Polycarbonates by Varying Melt Viscosity.

This work describes a new concept of porous vapor sensor materials based on co-continuous polycarbonate/poly(vinylidene fluoride)/multiwalled carbon nanotube (PC/PVDF/MWCNT) blend composites. The blend composites were fabricated by melt mixing in a one-step mixing process, and the MWCNT containing component (here PC) was extracted, leaving a MWCNT network on the continuous surface of the remaining component (here PVDF). First, by selecting three PCs with different molecular weights, the blend viscosity ratio and blend fineness and interfacial area were varied. At the chosen blend composition of 40/60 wt %, the desired co-continuous structure was achieved with MWCNTs selectively localized in PC. The conductive polymer composites (CPCs) with low-viscosity PC had the highest conductivity due to a combination of the best MWCNT dispersion and the coarsest blend morphology. The vapor sensing of CPC sensor materials with 1 wt % MWCNT was tested using saturated vapors of dichloromethane, acetone, tetrahydrofuran, and ethyl acetate, showing good interaction with PC. The compact compression molded CPC materials with low-viscosity PC showed the lowest relative resistance changes (Rrel) during the cyclic sensing tests, but a better recovery compared to corresponding CPCs with medium and high viscosity PC. The porous CPC sensors showed remarkable vapor sensing performance compared to the corresponding compact sensors with better sensing stability, reproducibility, and reversibility. Scanning electron microscopy (SEM) confirmed that a fraction of the nanotubes remained on the surface of the continuous, nonsoluble PVDF after PC extraction. The porous sensor material from which the low-viscosity PC was extracted showed the highest Rrel (e.g., around 1300% after 100 s immersion in acetone vapor) compared to all other organic vapors investigated. The difference in vapor measurement between compact and porous sensor materials was attributed to the different sensing mechanisms of polymer swelling for the compact and vapor absorption on the free CNT networks for the porous samples.