Carboxyl-terminated Butadiene Acrylonitrile Research Articles

1H NMR and 13C NMR Investigation of Microstructures of Carboxyl-Terminated Butadiene Acrylonitrile Rubbers

Two carboxyl-terminated butadiene acrylonitrile (CTBN) copolymers, named Lan-1 and Lan-2, were synthesized by solution radical polymerization. They had similar physical properties with the commercial sample Hycar1300×13, but had higher viscosity. The results of 1H NMR and 13C NMR revealed that Hycar1300×13 had more branched chains and more acrylonitrile-1,4 butadiene bonded units, but had lower acrylonitrile–acrylonitrile and acrylonitrile-1,2 butadiene bonded units, compared with Lan-1 and Lan-2. This improved the flexibility of the molecular chains of Hycar1300×13, and correspondingly decreased its viscosity.

Characterization of shape memory behaviour of CTBN-epoxy resin system

Novel epoxy based shape memory polymers (SMPs) were prepared by blending bifunctional epoxy resin with varying content (0, 5, 10 and 15 wt %) of Carboxyl-Terminated Butadiene Acrylonitrile (CTBN) rubber and cured with a cyclo-aliphatic amine hardener. The epoxy/CTBN blends were chemically characterized by epoxy content and gel time measurements. Neat resin castings were prepared for conducting shape memory tests. The glass transition temperature (Tg) of the test sample was measured in order to fix the deformation temperature (Ttrans). Shape memory (SM) cyclic tests were conducted on both unmodified and CTBN modified epoxy samples in order to comparatively assess their SM behavior. Compared to unmodified epoxy SMPs, the CTBN modified epoxy SMPs exhibited a significant increase in the number of SM cycles, which is attributed to the toughening effect of the CTBN phase.

Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

Carboxyl-modified multi-walled carbon nanotubes (MWCNT-COOHs) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN). The car- boxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg), mechanical properties, thermal stability and mor- phology of DGEBA/CTBN/MWCNT-COOHs nanocomposites were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), universal test machine, thermogravimetric analysis and scanning electron microscopy (SEM). DSC kinetic studies showed that the addition of MWCNT-COOHs accelerated the curing reaction of the rubber-toughened epoxy resin. DMA results revealed that Tg of rubber-toughened epoxy nanocomposites lowered with MWCNT-COOH contents. The tensile strength, elongation at break, flexural strength and flexural modulus of DGEBA/ CTBN/MWCNT-COOHs nanocomposites were increased at lower MWCNT-COOH concentration. A homogenous disper- sion of nanocomposites at lower MWCNT-COOH concentration was observed by SEM.

Effects of Rubber Addition to an Epoxy Resin and Its Fiber Glass‐Reinforced Composite

AbstractEpoxy resins are considered as one of the most important class of thermosetting polymers and find extensive use in various fields. However, these materials are characterized by a relatively low toughness. In this respect, many efforts have been made to improve the toughness of cured epoxy resins. In this work, samples of epoxy resin diglycidyl ether of bisphenol‐A and fiber glass‐reinforced composite of this polymer with and without liquid carboxyl‐terminated butadiene acrylonitrile (CTBN) copolymer were prepared to assess the effect of CTBN rubber on the properties of polymeric and composite laminate specimens. The addition of CTBN into the polymeric specimens led to a decrease in the glass transition temperature, fracture stress (from 70.39 to 56.34 MPa), and tensile elasticity modulus (from about 3.51 to 2.65 GPa), accompanied by an increase in elongation (from 2.47 to 5.64%). However, the degradation temperature of the polymeric system was not modified. Infrared analysis evidenced the occurrence of chemical reaction between the two components, and scanning electron microscopy results suggested rubber particles deformation as the prevailing toughening mechanism. The rubber addition in the composite specimens, promoted an increase simultaneous in fracture stress and in elongation at fracture. The elasticity tensile modulus has not changed. This probably results from the increased deformation capacity of the matrix, which prevents its premature cracking, and better adhesion between fibers and matrix observed in the CTBN‐modified composite laminates. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers

Epoxy Adhesives Modified With Nano- and Microparticles for In Situ Timber Bonding: Fracture Toughness Characteristics

Adhesives used for bonded-in steel or composite pultruded rods and plate to make connections in timber structures are commonly room temperature cure adhesives. The room temperature cure, applied without pressure, thixotropic, and shear thinning characteristics of the adhesives, is for ease of application when repairs and reinforcement are being made in situ in the field. The room temperature cure adhesive may not fully cross-link and this may cause brittleness. Therefore to improve the toughness properties of such adhesives, nanoparticles can be added. This paper reports the experimental investigation carried out on the fracture toughness of three thixotropic and room temperature cured epoxy-based adhesives formulated specifically for in situ timber bonding, namely, CB10TSS (standard adhesive), Albipox is CB10TSS with the addition of nanodispersed carboxyl-terminated butadiene acrylonitrile (CTBN), and Timberset is an adhesive formulation containing ceramic microparticles. The fracture toughness behavior of the adhesives was investigated using the Charpy impact test on unnotched and notched specimens conditioned at 20∘C/65%RH to evaluate notch sensitivity, and a single-edge notched beam (SENB) test was performed to evaluate the stress intensity factor KIC. The fracture surfaces were investigated using scanning electron microscopy. Under high impact rate, toughness was in the order of CB10TSS, Albipox, and Timberset. CB10TSS and Albipox were found to be ductile in the unnotched state and brittle when notched. Timberset was brittle in both unnotched and notched states. Under low strain rate (SENB) conditions the addition of CTBN significantly improved the fracture toughness of Albipox compared with CB10TSS and Timberset. Examination of the topography of the fractured surface revealed marked changes in crack propagation due to the addition of nano- or microfillers accounting for the variation in toughness properties.

Study on the Effect of Carboxyl Terminated Butadiene Acrylonitrile (CTBN) Copolymer Concentration on the Decomposition Kinetics Parameters of Blends of Glycidyl Epoxy and Non-Glycidyl Epoxy Resin

The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo gravimetric analysis (TGA) technique under a nitrogen atmosphere. The blends were prepared by physical mixing and were cured with diamine. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. From this value of reaction order, activation energy (E), and pre-exponential factor (Z) were calculated. It was found that the activation energy increased with the addition of liquid elastomer.

The toughening mechanism in hybrid epoxy-silica-rubber nanocomposites (HESRNs)

Two different size nanosilica (NS) particles, nominally 20 nm and 80 nm in diameter, and carboxyl terminated butadiene acrylonitrile (CTBN) were blended into a lightly crosslinked, DGEBA/piperidine epoxy system to investigate the toughening mechanisms in hybrid epoxy-silica-rubber nanocomposites (HESRNs). Adding small amount of NS particles into CTBN toughened epoxies further improved the fracture toughness to a level that could not be achieved by increasing CTBN content alone. Interestingly, this toughening effect is diminished when NS particles clustered at high CTBN contents. In addition, the effect of NS particle size on toughening behavior was not considerable, except the case when NS clustering is observed. According to the SEM and TOM investigations, the plastic zone, which consists of shear banding and matrix dilation, is further enlarged in front of the crack tip in HESRNs. Irwin’s model is used to evaluate the process zone concept and the result indicates that zone shielding is credited for the toughening mechanism in these HESRNs.

Toughening of epoxy using core–shell particles

An epoxy resin, cured using an anhydride hardener, has been modified by the addition of preformed core–shell rubber (CSR) particles which were approximately 100 or 300 nm in diameter. The glass transition temperature, T g, of the cured epoxy polymer was 145 °C. Microscopy showed that the CSR particles were well dispersed through the epoxy matrix. The Young’s modulus and tensile strength were reduced, and the glass transition temperature of the epoxy was unchanged by the addition of the CSR particles. The fracture energy increased from 77 J/m2 for the unmodified epoxy to 840 J/m2 for the epoxy with 15 wt% of 100-nm diameter CSR particles. The measured fracture energies were compared to those using a similar amount of carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. The CTBN particles provided a larger toughening effect when compared to CSR particles, but reduced the glass transition temperature of the epoxy. For the CSR-modified epoxies, the toughening mechanisms were identified using scanning electron microscopy of the fracture surfaces. Debonding of the cores of the CSR particles from the shells was observed, accompanied by plastic void growth of the epoxy and shell. The observed mechanisms of shear band yielding and plastic void growth were modelled using the Hsieh et al. approach (J Mater Sci 45:1193–1210). Excellent agreement between the experimental and the predicted fracture energies was found. This analysis showed that the major toughening mechanism, responsible for 80–90% of the increase in fracture energy, was the plastic void growth.

Fracture toughness of thixotropic and room temperature cured epoxy-based adhesives for in situ timber bonding

Abstracts An experimental investigation has been carried out on the fracture toughness of three thixotropic and room temperature cured epoxy-based adhesives formulated specifically for in situ timber bonding namely CB10TSS (standard adhesive), Albipox is a modification of CB10TSS with the addition of nano-dispersed carboxyl-terminated butadiene acrylonitrile (CTBN) and Timberset is a commercially used adhesive formulation containing quartz, mica and bentonite and cured with an aliphatic diamine (TMD). The fracture toughness behaviour of the adhesives was investigated using the Charpy impact test on unnotched specimens conditioned at 20 °C/65%RH and 30 °C/95%RH to observe the effect of temperature and moisture. The Charpy impact tests were also performed on notched specimens to evaluate notch sensitivity, and a single-edge notched beam (SENB) test was performed to evaluate the stress intensity factor, KIC. The fracture surfaces were investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Under high impact rate at 20 °C/65%RH, toughness was in the order of CB10TSS, Albino and Timber set. CB10TSS and Albino were found to be ductile in the unmatched state and brittle when notched. After exposure to 30 °C/95%RH, Albino was tougher than CB10TSS due to an increase in ductility, which allowed the rubber particles to cogitate. Timber set was brittle in both unmatched and notched states. Under low strain rate (SENB) conditions the addition of CTBN significantly improved the fracture toughness of Albino compared with CB10TSS and Timber set. Examination of the topography of the fractured surface revealed marked changes in crack propagation due to the addition of nana- or micro-fillers accounting for the variation in toughness properties. The toughness of thixotropic adhesives, specified for bonding in connections in timber structures, could therefore be enhanced by the inclusion in the epoxy matrix of phase separated liquid rubber.

Interfacial adhesion improvement of plain woven carbon fiber reinforced epoxy filled with micro-fibrillated cellulose by addition liquid rubber

In certain application of fiber reinforced polymer composites fracture resistance is required. The aim of this study was to improve the interfacial adhesion between plain woven carbon fiber (CF) and epoxy matrix filled with microfibrillated cellulose (MFC) modified with carboxyl-terminated butadiene acrylonitrile (CTBN) as liquid rubber. CF/Epoxy/MFC/CTBN composite was characterized by different techniques, namely, tensile, bending, fracture toughness (mode I) test, and scanning electron microscope (SEM). The results reveal that at a fiber content 1% of MFC and 10% CTBN, initiation and propagation interlaminar fracture toughness in mode I improved significantly by 96 and 127%, respectively, which could be attribute to strong adhesion between filled epoxy, CF, and rubber. This can be explained by SEM at given weight as well; SEM images showed that in front of the tip, fiber breakage during initiation delimination as well as the extensive matrix deformation between fibers accounting for increase fracture toughness.

Modification of dicyanate ester resin by liquid carboxyl-terminated butadiene acrylonitrile copolymer

Bisphenol A dicyanate ester (BADCy) was modified with liquid carboxyl-terminated butadiene acrylonitrile (LCTBN). The cured BADCy resin was formed through the cyclotrimerization of cyanate functional groups into triazine rings, and there was the chemical reaction between BADCy and LCTBN. Mechanical performance indicated that the introduction of LCTBN into BADCy resin improved the impact strength with maintenance in flexural strength. Scanning electron microscopy (SEM) showed that the pure resin had a smooth glassy fracture surface, whereas cured blends containing LCTBN showed rougher fracture surfaces, and exhibited enhanced impact resistance. The TEM observation showed that the two phases in the cured resins exhibit a good interaction adhesion. Thermograms of BADCy modified with LCTBN showed the little reduction of heat deflection temperature, and a reduction in thermal stability temperature by 30 K. Dynamic mechanical analysis (DMA) showed that the pure BADCy had higher storage modulus ( E′) values than that of the BADCy modified with LCTBN, whereas the loss modulus ( E″) was lower, and that the glass transition temperature (Tg) of modified BADCy was 229 °C and lower than that (249 °C) of pure BADCy resin.

Blends of cardanol-based epoxidized novolac resin and CTBN for application in surface coating: a study on thermal, mechanical, chemical, and morphological characteristics

Blend samples of cardanol-based epoxidized novolac resin and different weight percentages of carboxyl-terminated butadiene acrylonitrile (CTBN) were developed and cured with stoichiometric amounts of aliphatic amine. The formation of various products during the curing of blend samples has been studied by Fourier-transform infrared spectroscopy. The dynamic differential scanning calorimeter scans showed that the pure epoxies and their blend samples with CTBN cured in the temperature range of 100–150°C. The blend sample containing 15 wt% CTBN showed the least cure time (at 120°C) among all other blend samples. Upon evaluation, it was found that blend samples exhibit better properties compared to pure epoxy resin in terms of increase in impact strength and elongation-at-break of the casting and gloss, scratch hardness, adhesion, and flexibility of the film. The improvement in these properties indicates that the rubber modified resin would be more durable than the epoxy based on cardanol. Chemical and morphological properties of the formulated resins were also determined. The thermal stability of the blend samples containing 15 wt% CTBN in epoxy resin was the highest among all other prepared systems. The blend morphology, studied by scanning electron microscope, showed the presence of precipitated discrete rubber particles, which dispersed throughout the epoxy matrix—i.e., they revealed the presence of two-phase morphological features.

The toughness of epoxy polymers and fibre composites modified with rubber microparticles and silica nanoparticles

The present paper investigates the effect of adding silica nanoparticles to an anhydride-cured epoxy polymer in bulk and when used as the matrix of carbon- and glass-fibre reinforced composites. The formation of ‘hybrid’ epoxy polymers, containing both silica nanoparticles and carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber microparticles, is also discussed. The structure/property relationships are considered, with an emphasis on the toughness and the toughening mechanisms. The fracture energy of the bulk epoxy polymer was increased from 77 to 212 J/m2 by the presence of 20 wt% of silica nanoparticles. The observed toughening mechanisms that were operative were (a) plastic shear-yield bands, and (b) debonding of the matrix from the silica nanoparticles, followed by plastic void-growth of the epoxy. The largest increases in toughness observed were for the ‘hybrid’ materials. Here a maximum fracture energy of 965 J/m2 was measured for a ‘hybrid’ epoxy polymer containing 9 wt% and 15 wt% of the rubber microparticles and silica nanoparticles, respectively. Most noteworthy was the observation that these increases in the toughness of the bulk polymers were found to be transferred to the fibre composites. Indeed, the interlaminar fracture energies for the fibre-composite materials were increased even further by a fibre-bridging toughening mechanism. The present work also extends an existing model to predict the toughening effect of the nanoparticles in a thermoset polymer. There was excellent agreement between the predictions and the experimental data for the epoxy containing the silica nanoparticles, and for epoxy polymers containing micrometre-sized glass particles. The latter, relatively large, glass particles were investigated to establish whether a ‘nano-effect’, with respect to increasing the toughness of the epoxy bulk polymers, did indeed exist.

Thermal, tensile and morphological properties of gamma-ray irradiated epoxy-clay nanocomposites toughened with a liquid rubber

This paper describes the process of mixing carboxyl-terminated butadiene-acrylonitrile (CTBN) with nano-clay to improve the toughness and mechanical strength of bisphenol A type epoxy, which tends to exhibit brittle fracture behavior. For evaluation of the degradation by radiation, gamma rays of 500 kGy, 1000 kGy, and 1500 kGy were used to irradiate the samples at a dose rate of 8 kGy/hr. The molecular structure changes, inter-layer distance of the clay, morphology, and radiation degradation behavior of epoxy and CTBN of the gamma-ray irradiated samples were measured using a Fourier transform infrared spectrometer (FTIR), X-ray diffractometer (XRD), thermogravimetric analyzer (TGA), tensile machine and a field emission scanning electron microscope (FESEM). The FTIR results verified the band stretching of the –CN and the C O bonding in CTBN from the spectra of CTBN-modified epoxies. The XRD results verified the easy intercalation of clay added to the epoxy and CTBN. In the TGA experiment, as the absorption dose increased and the heating rate decreased, the thermogravimetry-derivative thermogravimetry (TG–DTG) curves of the samples rapidly decreased. As the absorption dose increased, the tensile strengths of all the degraded samples sharply decreased, and morphologies, which were rubber particles fractured by gamma rays, were observed by FESEM.

Experimental and computational investigations on strain rate sensitivity and deformation behavior of bulk materials made of epoxy resin structural adhesive

The deformation behavior and strain rate sensitivity of an epoxy resin structural adhesive and a CTBN (carboxyl-terminated butadiene-acrylonitrile)-modified epoxy resin adhesive are experimentally investigated using an INSTRON-type material testing machine and a split Hopkinson pressure bar apparatus. The experimental results show some fundamental features of a typical compressive stress–strain behavior of amorphous glassy polymers with linear elastic and nonlinear inelastic deformation stages. In the inelastic deformation, a peak stress and a strain-softening stage after the peak can be observed in the entire range of strain rate from 10 - 4 to 10 3 s - 1 . In addition, it can be found that the relationship between the peak stress and strain rate on a semi-logarithmic plot is linear in the range of low strain rate. However, the slope of the curve changes at a high strain rate, and the nonlinear behavior of the peak stress can be obtained against the strain rate. In order to describe such a nonlinear peak stress–strain rate relationship and the deformation behavior of the structural adhesives in a wide range of strain rate on the basis of the experimental results, a plastic shear strain rate is formulated. Then, a three-dimensional constitutive model is derived based on a four-elements model with an elastic series element by considering the adhesive to be a glassy polymer. The plastic deformation rate tensor is expressed by the effective stress, which is the difference between the total stress and back stress, and the plastic shear strain rate proposed here. The stress tensor can be obtained by solving nonlinear simultaneous equation. The formulated constitutive model is implemented into the commercial FE code, ABAQUS/Explicit, and then a computational simulation is performed. As a result, the validity of the proposed model is shown by comparing the experimental result.

Investigation of the fracture resistance in hoop wound composites modified with two different reactive oligomers

Rubber modification of hoop filament wound epoxy composites was investigated using amine-terminated butadiene acrylonitrile (ATBN) and carboxyl-terminated butadiene acrylonitrile (CTBN) oligomers. Both mechanical and physical properties of modified composites were investigated and the morphology of the samples was studied via scanning electron microscopy. Results indicated that, when added to the epoxy matrix, ATBN effected a superior increase in toughness, yet a more severe decline in compressive and flexural strength, compared to CTBN. In contrast, in the case of composite samples, incorporation of ATBN led to more favorable mechanical properties, from the viewpoint of both toughness and strength, relative to CTBN. This curious observation was generally attributed to the different amounts of rubber–epoxy precipitation and fiber–matrix adhesion, as well as various degrees of cavitation.

Studies on the physico-mechanical and thermal characteristics of blends of DGEBA epoxy, 3,4 epoxy cyclohexylmethyl, 3′,4′-epoxycylohexane carboxylate and carboxyl terminated butadiene co-acrylonitrile (CTBN)

Toughening of blend of diglycidyl ether of bisphenol-A (DGEBA) and 3,4 epoxy cyclohexylmethyl, 3′,4′-epoxycylohexane carboxylate, i.e. cycloaliphatic epoxy resin (CAE) with varying weight ratios (0–25 wt%) of carboxyl terminated butadiene acrylonitrile (CTBN) copolymer have been investigated. Fourier transform infrared (FTIR) spectroscopic analysis established that the interaction between oxirane groups of DGEBA, CAE and CTBN were responsible for characteristics peak shifts in the blends compared to their counterparts. Physico-mechanical properties of the prepared samples, e.g. tensile, flexural and impact strengths showed an optimum concentration of CTBN (15 wt%) into epoxy matrix, which offered maximum toughening. Thermal stability of the prepared samples was analyzed by dynamic thermogravimetric runs. Cross-sections of the cured samples which failed during impact testing have been critically studied through scanning electron microscopic (SEM) analysis to gain insight into the phase morphology.

Structure, Viscoelastic Properties and Damping Mechanisms of Reactive Butadiene-nitrile Rubber/Epoxy Polymer Blends

Carboxyl-terminated butadiene acrylonitrile (CTBN) rubber/ epoxy (diglycidyl ether of bisphenol-A) / diamino diphenyl methane polymer blends with 60 wt% of CTBN were formulated to evaluate the viscoelasticity and the damping properties. When the blend resins had micro-phase separated morphologies composed of epoxy-rich dispersed phases larger than 500 nm in diameter surrounded by a rubber-rich continuous phase, the loss factors (η) of the steel laminates adhered with the resin significantly depended on the environmental temperature and the resonant frequencies. The resins with epoxy-rich phases smaller than 200 nm in diameter had broad glass-transition temperature range that resulted in the high loss factor (η > 0.1) of the steel laminates in the broad temperature range. Inhomogeneous nano-gel structures with 20∼30 nm sizes were observed in more compatible resins by scanning probe microscopy, although appreciable micro-phase separation was detected by none of SEM and TEM. Pulse NMR suggested that the fraction of interfacial phase in the resins increased with increasing the compatibility of the blends. The large interfacial phase in the inhomogeneous nano-gel structures seems to play an important role in the damping mechanisms.

Effect of carboxyl‐terminated butadiene acrylonitrile copolymer concentration on mechanical and morphological features of binary blends of nonglycidyl‐type epoxy resins

AbstractBlend samples were prepared by physical blending of nonglycidyl‐type epoxy resin with varying weight ratios of carboxyl‐terminated butadiene acrylonitrile (CTBN) copolymer ranging between 0 and 25 wt%. The blend samples were cured with stoichiometric quantity of diamine. A comparative study of prepared blend samples by Fourier transform infrared (FTIR) spectroscopy showed the modification as a result of chemical reactions between cycloaliphatic epoxy, CTBN, and 4,4′‐diamino diphenyl sulfone. The impact strength of the blend systems increased up to 15 wt% addition of CTBN in the blend and decreased thereafter. The toughness and elongation at break increased, whereas tensile strength decreased up to 20 wt% loading of CTBN in the blends. Two‐phase morphology appeared with the incorporation of CTBN in the cycloaliphatic epoxy resin matrix. © 2008 Wiley Periodicals, Inc. Adv Polym Techn 26:258–271, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20106

Molecular assembled self-doped polyaniline copolymer ultra-thin films

A self-assembly technique and copolymerization were used to buildup a self-doped polyaniline (SPANI) ultra-thin film on an indium-tin oxide (ITO) substrate. The monomers used were aniline and its derivative MSAN ( m-aminobenzenesulfonic acid). Successful MSAN/AN copolymerization and film formation were simultaneously performed in aqueous solution with the addition of oxidant (APS, ammonium persulfate). The film deposition rate of a high AN/MSAN ratio system is generally higher than that of a low AN/MSAN ratio system. Cyclic voltammetry, UV–vis spectroscopy, and α-step instruments indicate a systematic dependence of the film thickness of these ultra-thin films on the assembly time and temperatures. The Auger depth profile reveals the elemental distribution in these films and exhibits different deposition rates between AN and MSAN. XPS N 1s spectra also show the variation of the degree of doping. This SPANI film can be used as an electrochromic electrode in a corresponding device. Carboxyl-terminated-butadiene-acrylonitrile (CTBN) blended with LiClO 4 was used as a solid polymer electrolyte. A total solid electrochromic device was assembled as ITO/SPANI/LiClO 4–CTBN/PEDOT:PSS/ITO, where PEDOT:PSS is poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) as the counter complementary electrode. The device was pale gray at −1.5 V and blue at +1.5 V.