Stable ink dispersions suitable for roll-to-roll printing with sensitivity towards hydrogen sulphide gas

Abstract This work describes the development of a stable dispersion which is suitable for roll-to-roll printing of a film exhibiting hydrogen sulfide (H2S) gas sensing functionality. The dispersions are made from copper chloride in combination with either citric acid or citric acid and polyaniline (PANI). Aqueous PANI dispersions together with copper chloride (CC) have been shown to have H2S sensing properties, but the dispersion gets unstable with the addition of CC within a pH range from 5 to 8. In this study, a mixture of CC and citric acid (CA) was optimized for printability as well as for sensitivity towards H2S gas. Furthermore the stability of an aqueous PANI dispersion was studied after the addition of CC or a CC–CA mixture as a function of pH. The stable dispersions were printed on top of flexographically printed interdigitated silver electrodes and their sensitivity towards 10 ppm H2S was verified by following the change in resistance. The printed films were characterized by atomic force microscope (AFM), time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and conductometry. The sensors showed almost a three orders of magnitude change in resistance upon exposure to 10 ppm H2S at ambient conditions.

[1]  Fabienne Poncin-Epaillard,et al.  Polyaniline as a new sensitive layer for gas sensors , 2003 .

[2]  Bonn,et al.  Viscous fingering in a yield stress fluid , 2000, Physical review letters.

[3]  B. H. Weiller,et al.  Polyaniline nanofiber composites with metal salts: chemical sensors for hydrogen sulfide. , 2005, Small.

[4]  A. MacDiarmid,et al.  "Synthetic Metals": A Novel Role for Organic Polymers (Nobel Lecture). , 2001, Angewandte Chemie.

[5]  Petri Ihalainen,et al.  Biocompatibility of printed paper-based arrays for 2-D cell cultures. , 2013, Acta biomaterialia.

[6]  G. Graffmann,et al.  Schnelle Bestimmung von Citrat in Wasch‐ und Reinigungsmitteln durch Titration mit Cu‐Lösung , 1974 .

[7]  Anjali A. Athawale,et al.  Chloroform vapour sensor based on copper/polyaniline nanocomposite , 2002 .

[8]  R. C. Weast CRC Handbook of Chemistry and Physics , 1973 .

[9]  J. Popp,et al.  A critical review of the literature on hydrogen sulfide toxicity. , 1984, Critical reviews in toxicology.

[10]  S. Semancik,et al.  Mesoporous nanoparticle TiO2 thin films for conductometric gas sensing on microhotplate platforms , 2006 .

[11]  Daniel T. Haworth,et al.  Determination of stability constants of a copper/citric acid complex by ion-exchange chromatography and atomic absorption spectrometry , 1987 .

[12]  M. Toivakka,et al.  Printability of functional inks on multilayer curtain coated paper , 2013 .

[13]  Petri Ihalainen,et al.  Printed hydrogen sulfide gas sensor on paper substrate based on polyaniline composite , 2013 .

[14]  Terrence B. Field,et al.  Composition and Stability of Iron and Copper Citrate Complexes in Aqueous Solution , 1974 .

[15]  P. Rannou,et al.  Poly(aniline) doped with 5-formyl-2-furansulfonic acid: A humidity memory , 2010 .

[16]  Andrew P. Monkman,et al.  Polyaniline thin films for gas sensing , 1995 .

[17]  Karl Crowley,et al.  An aqueous ammonia sensor based on an inkjet-printed polyaniline nanoparticle-modified electrode. , 2008, The Analyst.

[18]  A. J. Francis,et al.  Biodegradation of metal citrate complexes and implications for toxic-metal mobility , 1992, Nature.

[19]  Martti Toivakka,et al.  A multilayer coated fiber-based substrate suitable for printed functionality , 2009 .

[20]  Kun-Lin Yang,et al.  Detecting hydrogen sulfide by using transparent polymer with embedded CdSe/CdS quantum dots , 2010 .

[21]  R. W. Parry,et al.  Citrate Complexes of Copper in Acid Solutions , 1952 .

[22]  Petri Ihalainen,et al.  Printed copper acetate based H2S sensor on paper substrate , 2012 .

[23]  Mang Wang,et al.  Preparation of water soluble poly(aniline) and its gas-sensitivity , 2005 .

[24]  Dinesh K. Aswal,et al.  Sub-ppm H2S sensing at room temperature using CuO thin films , 2010 .

[25]  Gordon G Wallace,et al.  Fabrication of Polyaniline-Based Gas Sensors Using Piezoelectric Inkjet and Screen Printing for the Detection of Hydrogen Sulfide , 2010, IEEE Sensors Journal.

[26]  Ronald Österbacka,et al.  Low-Cost Hydrogen Sulfide Gas Sensor on Paper Substrates: Fabrication and Demonstration , 2012 .

[27]  B. H. Weiller,et al.  Direct electrical measurement of the conversion of metal acetates to metal sulfides by hydrogen sulfide. , 2006, Inorganic chemistry.

[28]  Anuvat Sirivat,et al.  Electrical conductivity of polyaniline/zeolite composites and synergetic interaction with CO , 2005 .