Novel polymeric humidity sensors based on sulfonated poly (ether ether ketone)s: Influence of sulfonation degree on sensing properties

Abstract Sulfonated poly (ether ether ketone)s (SPEEKs) with different values of sulfonation degree were successfully synthesized by a direct aromatic nucleophilic substitution polymerization of sulfonated monomers. By the direct-synthesis method, the number of sulfonic acid groups can be precisely controlled. They were then fabricated by spin coating on a ceramic substrate to be used as a novel polymeric humidity sensor. The morphology of the ionic polymers especially the microstructure of ionic clusters, water sorption and the complex impedance spectra of the sensors were investigated to explain the humidity sensing characteristics and the sensing mechanism under different relative humidity. In addition, SPEEK-6 polymer with sulfonation degree (D s  = 1.18) was chosen as the optimal humidity sensing materials, which possessed high sensitivity and satisfactory linearity ranging from 11% RH to 97% RH. Furthermore, it exhibited a small hysteresis (less than 3% RH) during the sorption processes, an acceptable response/recovery time (100 s response and 105 s of recovery time) and an excellent repeatability. These results indicated SPEEKs could be promising for applications in humidity sensor.

[1]  Jianxun Zhao,et al.  Micro humidity sensors based on ZnO–In2O3 thin films with high performances , 2012 .

[2]  H. Na,et al.  A novel highly sensitive humidity sensor derived from sulfonated poly(ether ether ketone) with metal salts-ion substitution , 2016 .

[3]  Takaomi Kobayashi,et al.  A novel highly sensitive humidity sensor based on poly(pyrrole-co-formyl pyrrole) copolymer film: AC and DC impedance analysis , 2015 .

[4]  Yang Li,et al.  Water-soluble polyaniline and its composite with poly(vinyl alcohol) for humidity sensing , 2010 .

[5]  Mujie Yang,et al.  Investigations on the ion transport mechanism in conducting polymer films , 2000 .

[6]  Chi-En Lu,et al.  Humidity Sensors: A Review of Materials and Mechanisms , 2005 .

[7]  H. Na,et al.  Preparation and properties of novel cross-linked sulfonated poly(arylene ether ketone) for direct methanol fuel cell application , 2010 .

[8]  Adhesives: a new class of polymer coatings for surface acoustic wave sensors for fast and reliable process control applications , 2001 .

[9]  C. Mallika,et al.  Zinc(II) oxide-zinc(II) molybdate composite humidity sensor , 2002 .

[10]  A. Eisenberg.  Clustering of Ions in Organic Polymers. A Theoretical Approach , 1970 .

[11]  H. Kita,et al.  Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application. 1. Synthesis, Proton Conductivity, and Water Stability of Polyimides from 4,4‘-Diaminodiphenyl Ether-2,2‘-disulfonic Acid , 2002 .

[12]  Pasqualina M. Sarro,et al.  Relative humidity sensors using porous SiC membranes and Al electrodes , 2004 .

[13]  Y. Li,et al.  Humidity sensors using in situ synthesized sodium polystyrenesulfonate/ZnO nanocomposites. , 2004, Talanta.

[14]  H. Kita,et al.  Water-resistant humidity sensors based on sulfonated polyimides , 2007 .

[15]  M. Matsuguchi,et al.  Humidity sensor durable at high humidity using simultaneously crosslinked and quaternized poly(chloromethyl styrene) , 1995 .

[16]  Tse-Chuan Chou,et al.  Gold-solid polymer electrolyte sensor for detecting dissolved oxygen in water , 2000 .

[17]  Seung-Hyeon Moon,et al.  Electrochemical characterization of sulfonated poly(arylene ether sulfone) (S-PES) cation-exchange membranes , 2003 .

[18]  John T.W. Yeow,et al.  Carbon nanotube-enhanced capillary condensation for a capacitive humidity sensor , 2006 .

[19]  Xianfeng Li,et al.  Influence of the hydroquinone with different pendant groups on physical and electrochemical behaviors of directly polymerized sulfonated poly(ether ether sulfone) copolymers for proton exchange membranes , 2006 .

[20]  Xianfeng Li,et al.  Direct synthesis of sulfonated aromatic poly(ether ether ketone) proton exchange membranes for fuel cell applications , 2004 .

[21]  Michael A. Hickner,et al.  Direct polymerization of sulfonated poly(arylene ether sulfone) random (statistical) copolymers: candidates for new proton exchange membranes , 2002 .

[22]  Peggy Cebe,et al.  Effect of thermal history on mechanical properties of polyetheretherketone below the glass transition temperature , 1987 .

[23]  A. Samui,et al.  All-solid supercapacitor based on polyaniline and sulfonated poly(ether ether ketone) , 2003 .

[24]  B. Adhikari,et al.  Polymers in sensor applications , 2004 .

[25]  Yoichi M. A. Yamada,et al.  An assembled complex of palladium and non-cross-linked amphiphilic polymer: a highly active and recyclable catalyst for the Suzuki-Miyaura reaction. , 2002, Organic letters.

[26]  B. Van der Bruggen,et al.  Chemical modification of polyethersulfone nanofiltration membranes: A review , 2009 .

[27]  Changpeng Liu,et al.  Preparation and characterization of sulfonated poly(ether ether ketone ketone) proton exchange membranes for fuel cell application , 2005 .

[28]  Desheng Jiang,et al.  Quartz crystal microbalance coated with carbon nanotube films used as humidity sensor , 2005 .

[29]  Se Young Oh,et al.  Synthesis and characterization of sulfonated polyimide membranes for direct methanol fuel cell , 2003 .

[30]  H. Kita,et al.  Synthesis and properties of highly sulfonated proton conducting polyimides from bis(3-sulfopropoxy)benzidine diamines , 2004 .

[31]  H. Na,et al.  Blend membranes based on disulfonated poly(aryl ether ether ketone)s (SPEEK) and poly(amide imide) (PAI) for direct methanol fuel cell usages , 2007 .

[32]  D. Yan,et al.  Synthesis of sulfonated poly(phthalazinone ether sulfone)s by direct polymerization , 2002 .

[33]  P. Ghosh,et al.  Surface modification of ultrafiltration membranes by preadsorption of a negatively charged polymer I. Permeation of water soluble polymers and inorganic salt solutions and fouling resistance properties , 2003 .

[34]  K. S. Dhathathreyan,et al.  Compact and flexible hydrocarbon polymer sensor for sensing humidity in confined spaces , 2014 .

[35]  R. Wu,et al.  The application of CNT/Nafion composite material to low humidity sensing measurement , 2005 .

[36]  K. Vijayamohanan,et al.  Humidity sensing properties of surface functionalised polyethylene and polypropylene films , 2002 .

[37]  Yang Li,et al.  Humidity sensitive properties of crosslinked and quaternized poly(4-vinylpyridine-co-butyl methacrylate) , 2005 .

[38]  Jiping Xu,et al.  Sodium sulfonate-functionalized poly(ether ether ketone)s , 1998 .

[39]  M. Cakmak,et al.  Crystallization phenomena in the injection molding of poly ether ether ketone and its influence on mechanical properties , 1990 .

[40]  Tong Zhang,et al.  Stable cross-linked amphiphilic polymers from a one-pot reaction for application in humidity sensors , 2016 .

[41]  H. Na,et al.  Novel humidity sensitive materials derived from naphthalene-based poly (arylene ether ketone) containing sulfobutyl pendant groups , 2016 .

[42]  Zhe Wang,et al.  SPEEKK/polyaniline (PANI) composite membranes for direct methanol fuel cell usages , 2006 .

[43]  Zhaoxiong Xie,et al.  High-sensitivity humidity sensor based on a single SnO(2) nanowire. , 2007, Journal of the American Chemical Society.

[44]  G. Robertson,et al.  Sulfonated Poly(aryl ether ketone)s Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direct Copolymerization, as Proton Exchange Membranes for Fuel Cell Application† , 2004 .

[45]  Yoshiro Sakai,et al.  Optical humidity sensing characteristics of Nafion—dyes composite thin films , 1992 .

[46]  Alain Giani,et al.  Porous silicon layer coupled with thermoelectric cooler: a humidity sensor , 2000 .

[47]  Murthy Chavali,et al.  Composite of TiO2 nanowires and Nafion as humidity sensor material , 2006 .

[48]  M. Matsuguchi,et al.  Improvements in the long-term stability of a LiCl dew-point sensor using cross-linked porous poly(vinyl alcohol) film , 2004 .

[49]  M. A. Gómez,et al.  Thermal properties, structure and morphology of PEEK/thermotropic liquid crystalline polymer blends , 2003 .

[50]  Tong Zhang,et al.  Synthesis and humidity sensitive property of cross-linked water-resistant polymer electrolytes , 2015 .

[51]  M. Guiver,et al.  Synthesis and characterization of carboxylated polysulfones , 1990 .

[52]  Rero M. Rubinger,et al.  Sulfonated polystyrene polymer humidity sensor: Synthesis and characterization , 2007 .

[53]  A. Marcelis,et al.  Intrinsic and Ionic Conduction in Humidity-Sensitive Sulfonated Polyaniline , 2014 .

[54]  Y. Sadaoka,et al.  Optochemical HCl gas detection using alkoxy substituted tetraphenylporphyrin-polymer composite films: Effects of alkoxy chain length on sensing characteristics , 2001 .

[55]  Yukari Sato,et al.  Use of a siloxane polymer for the preparation of amperometric sensors: O2 and NO sensors and enzyme sensors , 2001 .

[56]  P. Su,et al.  Flexibility and electrical and humidity-sensing properties of diamine-functionalized graphene oxide films , 2015 .

[57]  O. Inganäs,et al.  Small band gap polymers synthesized via a modified nitration of 4,7-dibromo-2,1,3-benzothiadiazole. , 2010, Organic letters.

[58]  J Wang,et al.  Processible polyaniline as an advanced potentiometric pH transducer. Application to biosensors. , 1999, Analytical chemistry.

[59]  Mingyao Zhang,et al.  Physical and electrochemical behaviors of directly polymerized sulfonated poly(arylene ether ketone sulfone)s proton exchange membranes with different backbone structures , 2009 .