Electrical Percolation Threshold and Size Effects in Polyvinylpyrrolidone-Oxidized Single-Wall Carbon Nanohorn Nanocomposite: The Impact for Relative Humidity Resistive Sensors Design

This paper reports, for the first time, on the electrical percolation threshold in oxidized carbon nanohorns (CNHox)–polyvinylpyrrolidone (PVP) films. We demonstrate—starting from the design and synthesis of the layers—how these films can be used as sensing layers for resistive relative humidity sensors. The morphology and the composition of the sensing layers are investigated through Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and RAMAN spectroscopy. For establishing the electrical percolation thresholds of CNHox in PVP, these nanocomposite thin films were deposited on interdigitated transducer (IDT) dual-comb structures. The IDTs were processed both on a rigid Si/SiO2 substrate with a spacing of 10 µm between metal digits, and a flexible substrate (polyimide) with a spacing of 100 µm. The percolation thresholds of CNHox in the PVP matrix were equal to (0.05–0.1) wt% and 3.5 wt% when performed on 10 µm-IDT and 100 µm-IDT, respectively. The latter value agreed well with the percolation threshold value of about 4 wt% predicted by the aspect ratio of CNHox. In contrast, the former value was more than an order of magnitude lower than expected. We explained the percolation threshold value of (0.05–0.1) wt% by the increased probability of forming continuous conductive paths at much lower CNHox concentrations when the gap between electrodes is below a specific limit. The change in the nanocomposite’s longitudinal Young modulus, as a function of the concentration of oxidized carbon nanohorns in the polymer matrix, is also evaluated. Based on these results, we identified a new parameter (i.e., the inter-electrode spacing) affecting the electrical percolation threshold in micro-nano electronic devices. The electrical percolation threshold’s critical role in the resistive relative-humidity sensors’ design and functioning is clearly emphasized.

[1]  Bumsuk Kim,et al.  Electrical properties of single-wall carbon nanotube and epoxy composites , 2003 .

[2]  S. Vicini,et al.  Investigation of the Mechanical and Dynamic-Mechanical Properties of Electrospun Polyvinylpyrrolidone Membranes: A Design of Experiment Approach , 2020, Polymers.

[3]  I. Kinloch,et al.  Ultra-low electrical percolation threshold in carbon-nanotube-epoxy composites , 2003 .

[4]  Dong Wang,et al.  Electrospun porous carbon nanofibers @ SnOx nanocomposites for high-performance supercapacitors: Microstructures and electrochemical properties , 2021 .

[5]  Pj Piet Lemstra,et al.  Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique , 2006 .

[6]  M. Yudasaka,et al.  Nano-aggregates of single-walled graphitic carbon nano-horns , 1999 .

[7]  Nam Ki Min,et al.  Novel resistive-type humidity sensor based on multiwall carbon nanotube/polyimide composite films , 2010 .

[8]  Guangliang Chen,et al.  Multi-walled carbon nanotubes reinforced nylon 6 composites , 2006 .

[9]  O. Buiu,et al.  CARBON NANOHORNS AND THEIR NANOCOMPOSITES: SYNTHESIS, PROPERTIES AND APPLICATIONS. A CONCISE REVIEW , 2018 .

[10]  T. Ebbesen,et al.  Exceptionally high Young's modulus observed for individual carbon nanotubes , 1996, Nature.

[11]  O. Buiu,et al.  Ternary Carbon-Based Nanocomposite as Sensing Layer for Resistive Humidity Sensor , 2019, Proceedings.

[12]  S. Blazewicz,et al.  Manufacturing and physico-mechanical characterization of carbon nanohorns/polyacrylonitrile nanocomposites , 2011, Journal of Materials Science.

[13]  Guobao Xu,et al.  Single-walled carbon nanohorns and their applications. , 2010, Nanoscale.

[14]  R. Kumar,et al.  Nanocomposite matrix conjugated with carbon nanomaterials for photocatalytic wastewater treatment. , 2020, Journal of hazardous materials.

[15]  L. Nicolais,et al.  Electrical Properties of Single Walled Carbon Nanotube Reinforced Polystyrene Composites , 2007 .

[16]  Noriaki Sano,et al.  Application of dielectrophoresis to fabrication of carbon nanohorn gas sensor , 2006 .

[17]  O. Buiu,et al.  Organic–Inorganic Ternary Nanohybrids of Single-Walled Carbon Nanohorns for Room Temperature Chemiresistive Ethanol Detection , 2020, Nanomaterials.

[18]  P. Avouris,et al.  Mechanical Properties of Carbon Nanotubes , 2001 .

[19]  Y. Candau,et al.  Electrical and thermophysical behaviour of PVC-MWCNT nanocomposites , 2008 .

[20]  E. Sani,et al.  Potential of carbon nanohorn-based suspensions for solar thermal collectors , 2011 .

[21]  J. A. Moreira,et al.  High-performance graphene-based carbon nanofiller/polymer composites for piezoresistive sensor applications , 2017 .

[22]  O. Buiu,et al.  Room Temperature Chemiresistive Ethanol Detection by Ternary Nanocomposites of Oxidized Single Wall Carbon Nanohorn (ox-SWCNH) , 2020, 2020 International Semiconductor Conference (CAS).

[23]  J. Zha,et al.  Complementary percolation characteristics of carbon fillers based electrically percolative thermoplastic elastomer composites , 2011 .

[24]  M. H. Rubinstein,et al.  The mechanical properties of some binders used in tableting , 1974, The Journal of pharmacy and pharmacology.

[25]  O. Buiu,et al.  Oxidized Carbon Nanohorn-Hydrophilic Polymer Nanocomposite as the Resistive Sensing Layer for Relative Humidity , 2020, Analytical Letters.

[26]  Rémy Dendievel,et al.  Viscoelastic behavior and electrical properties of flexible nanofiber filled polymer nanocomposites. Influence of processing conditions , 2007 .

[27]  M. Baeza,et al.  0D polymer nanocomposite carbon-paste electrodes using carbon nanohorns: Percolating networks, electrochemical achievements and filler comparison , 2020 .

[28]  Concepción Domingo,et al.  Low Percolation Threshold in Nanocomposites Based on Oxidized Single Wall Carbon Nanotubes and Poly(butylene terephthalate) , 2004 .

[29]  A. Afzal,et al.  Fabrication, characterization, morphological and thermal investigations of functionalized multi-walled carbon nanotubes reinforced epoxy nanocomposites , 2021 .

[30]  Shouke Yan,et al.  Morphology and electrical conductivity of polyethylene/polypropylene blend filled with thermally reduced graphene oxide and surfactant exfoliated graphene , 2017 .

[31]  Y. Hayashi,et al.  Synthesis of solvent-free conductive and flexible cellulose–carbon nanohorn sheets and their application as a water vapor sensor , 2020, Materials Research Express.

[32]  Y. Mai,et al.  Anomalous electrical conductivity and percolation in carbon nanotube composites , 2008 .

[33]  P. Pissis,et al.  Gas sensing properties of conductive polymer nanocomposites , 2011 .

[34]  O. Buiu,et al.  Electrical Percolation Threshold In Oxidized Single Wall Carbon Nanohorn-Polyvinylpyrrolidone Nanocomposite: A Possible Application For High Sensitivity Resistive Humidity Sensor , 2020, 2020 International Semiconductor Conference (CAS).

[35]  A. Chatterjee A model for the elastic moduli of three-dimensional fiber networks and nanocomposites , 2006 .

[36]  K. Rhee,et al.  Dependence of mechanical performances of polymer/carbon nanotubes nanocomposites on percolation threshold , 2018 .

[37]  Sabu Thomas,et al.  Recent developments on nanocellulose reinforced polymer nanocomposites: A review , 2017 .

[38]  K. Schulte,et al.  Two percolation thresholds in carbon nanotube epoxy composites , 2007 .

[39]  W. Bauhofer,et al.  A review and analysis of electrical percolation in carbon nanotube polymer composites , 2009 .

[40]  Q. Fu,et al.  The preparation of the poly(vinyl alcohol)/graphene nanocomposites with low percolation threshold and high electrical conductivity by using the large-area reduced graphene oxide sheets , 2013 .

[41]  S. Kundalwal Review on Modeling of Mechanical and Thermal Properties of Nano- and Micro-Composites , 2017, 1708.00764.

[42]  J. C. Halpin,et al.  Effects of Environmental Factors on Composite Materials. , 1969 .

[43]  J. Suehiro,et al.  Gas sensor using single-wall carbon nanohorns , 2007 .

[44]  Hideki Tanaka,et al.  Conductive and mesoporous single-wall carbon nanohorn/organic aerogel composites. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[45]  K. Dharamvir,et al.  Elastic moduli of carbon nanohorns , 2011 .

[46]  Waseem Sabir Khan,et al.  Electrical and Thermal Characterization of Electrospun PVP Nanocomposite Fibers , 2013 .

[47]  J. Barkauskas,et al.  Investigation of conductometric humidity sensors. , 1997, Talanta.

[48]  P. Ma,et al.  Correlations between Percolation Threshold, Dispersion State, and Aspect Ratio of Carbon Nanotubes , 2007 .

[49]  Guangjun Hu,et al.  Low percolation thresholds of electrical conductivity and rheology in poly(ethylene terephthalate) through the networks of multi-walled carbon nanotubes , 2006 .

[50]  M. Z. Akop,et al.  Comparison Between Functionalized Graphene and Carbon Nanotubes , 2019, Functionalized Graphene Nanocomposites and their Derivatives.

[51]  A. V. Gusel’nikov,et al.  Percolative Composites with Carbon Nanohorns: Low-Frequency and Ultra-High Frequency Response , 2019, Materials.

[52]  Rajagopal Ramasubramaniam,et al.  Homogeneous carbon nanotube/polymer composites for electrical applications , 2003 .

[53]  S. Maiti,et al.  Carbon nanohorn and graphene nanoplate based polystyrene nanocomposites for superior electromagnetic interference shielding applications , 2015 .

[54]  M. Yudasaka,et al.  Carbon nanohorns as anticancer drug carriers. , 2005, Molecular pharmaceutics.

[55]  S. Abd-El-Messieh,et al.  Electrical and mechanical properties of acrylonitrile rubber and linear low density polyethylene composites in the vicinity of the percolation threshold , 2009 .

[56]  Ö. Pekcan,et al.  Conductivity percolation of carbon nanotubes (CNT) in polystyrene (PS) latex film , 2010 .

[57]  C. Ewels,et al.  Structure, Properties, Functionalization, and Applications of Carbon Nanohorns. , 2016, Chemical reviews.

[58]  O. Buiu,et al.  Oxidized Carbon Nanohorns as Novel Sensing Layer for Resistive Humidity Sensor. , 2020, Acta chimica Slovenica.

[59]  R. Ansari,et al.  Analytical formulation for electrical conductivity and percolation threshold of epoxy multiscale nanocomposites reinforced with chopped carbon fibers and wavy carbon nanotubes considering tunneling resistivity , 2019, Composites Part A: Applied Science and Manufacturing.

[60]  J. Zou,et al.  Dispersion of carbon nanotubes and polymer nanocomposite fabrication using trifluoroacetic acid as a co-solvent , 2007 .