ABSTRACT DESIGN, SYNTHESIS AND ELECTROPOLYMERIZATION OF A NEW CHEMILUMINESCENT TERTHIENYL SYSTEM Atilgan, Nurdan M.Sc. Department of Chemistry Supervisor: Prof. Dr. Ahmet M. &Ouml / nal Co-Supervisor: Assist. Prof. Dr. Atilla Cihaner September 2008, 57 pages A novel monomer, possessing chemiluminescence properties, 5,7-di-ethylenedioxythiophen-2-yl-2,3-dihydro-thieno[3,4-d]pyridazine-1,4-dione (ETE-Lum) was synthesized. Chemiluminescence properties of ETE-Lum were investigated in alkaline water solution in the presence of H2O2 and this reaction was catalyzed by Fe+3 ion and blood. This study submits a new opportunity to investigate forensic and analytical application instead of 5-amino-2,3-dihydro-1,4-phthalazine-dione (luminol). Response of other metalic cations was also investigated under the same reaction conditions. Electrochemical properties of ETE-Lum were studied in 0.1 M acetonitrile/tetrabutylammonium perchlorate solvent system containing BF3-Et2O and also in neat BF3-Et2O solution. In addition, the corresponding polymer film of ETE-Lum (PETE-Lum) was synthesized successfully via repetitive cycling by cyclic voltammetry and its electrochemical properties were investigated in a monomer-free electrolyte solution. Spectroelectrochemical behavior of the polymer film on indium tin oxide working electrode was also investigated by recording the electronic absorption spectra, in-situ, in monomer-free electrolyte solution at different potentials. Furthermore, spectroelectrochemical studies revealed that PETE-Lum had an electronic band gap of 1.66 eV. The results of electrochemical and electroluminesence measurements indicated that chemiluminecent unit of monomer was protected during polymerization. In addition, PETE-Lum film was found to be electrochemiluminescence active, maintaining its activitiy over 1000 cycles.

In smart textiles, electrical conductivity is often required for several functions, especially contacting (electroding) and interconnecting. This thesis explores electrically conductive textile surfaces made by combining conventional textile coating methods with the intrinsically conductive polymer complex poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS). PEDOT:PSS was used in textile coating formulations including polymer binder, ethylene glycol (EG) and rheology modifier. Shear viscometry was used to identify suitable viscosities of the formulations for each coating method. The coating methods were knife coating, pad coating and screen printing. The first part of the work studied the influence of composition of the coating formulation, the amount of coating and the film formation process on the surface resistivity and the surface appearance of knife-coated textiles. The electrical resistivity was largely affected by the amount of PEDOT:PSS in the coating and indicated percolation behaviour within the system. Addition of a high-boiling solvent, i.e. EG, decreased the surface resistivity with more than four orders of magnitude. Studies of tear strength and bending rigidity showed that textiles coated with formulations containing larger amounts of PEDOT:PSS and EG were softer, more ductile and stronger than those coated with formulations containing more binder. The coated textiles were found to be durable to abrasion and cyclic strain, as well as quite resilient to the harsh treatment of shear flexing. Washing increased the surface resistivity, but the samples remained conductive after five wash cycles. The second part of the work focused on using the coatings to transfer the voltage signal from piezoelectric textile fibres; the coatings were first applied using pad coating as the outer electrode on a woven sensor and then as screen-printed interconnections in a sensing glove based on stretchy, warp-knitted fabric. Sensor data from the glove was successfully used as input to a microcontroller running a robot gripper. These applications showed the viability of the concept and that the coatings could be made very flexible and integrated into the textile garment without substantial loss of the textile characteristics. The industrial feasibility of the approach was also verified through the variations of coating methods.