Networks and blends of polyaniline and polyurethane: correlations between composition and thermal, dynamic mechanical and electrical properties

The combination of the electrical conducting properties of polyaniline (Pani) with the mechanical performance of polyurethanes (PU) was accomplished through the interconnection of the two polymers via condensation of a NCO terminated PU prepolymer and the amine groups of polyaniline. The crosslinking density of the resulting networks was set by the proportion between the two components, since the PU length was kept constant (M_w=40,000, M_n=23,000). The composition range Pani/PU spanned from 1 to 30%. Blends of the same composition were prepared for comparison purposes. Taking into account the IR absorption shifts, DMTA spectra, electrical conductivity results and computer generated optimized chain conformation, a morphological interpretation is proposed in which Pani chains form a continuous percolating phase dispersed in a polyurethane matrix, linked together by an interphase, with a certain degree of miscibility. This interphase would be responsible for the connectivity between the two components and the good mechanical properties observed. Electrical conductivity of the networks was in the 10⁻⁴ S/cm range.     

Preparation and Characterization of Electroconductive Adhesives of NanoG/Polyurethane-Epoxy IPNs

Polyurethanes (PU) based on toluene diisocyanate (TDI) and polypropylene glycol 2000 (PPG) were reacted with an epoxy resin (EP) to prepare interpenetrating polymer networks (IPNs). Three kinds of electroconductive adhesives were prepared by dispersing nano-graphite (NanoG) into different matrices, i.e., pure PU, crosslinked PU/EP, and pure EP. The effects of epoxy content on morphological structure, conducting properties, thermal stability, and adhesive properties of the electroconductive adhesives were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, standard digital multimeter, dynamic mechanical thermal analysis, and lapshear tests. The results indicate that epoxy in the polyurethane-epoxy IPN adhesives plays an important role in clanging the morphological structure and improving conductivity properties, thermal stability, and adhesive properties of the electroconductive adhesives of PU.     

Structure‐property relationship in polyaniline‐filled castor oil based chain extended polyurethanes

A series of polyaniline (Pani)‐filled chain extended polyurethanes (PUs) were prepared by condensation polymerization of castor oil with methylene diisocyanate (MDI) as crosslinker and diamino diphenyl sulfone (DDS) as chain extender. The effect of different amounts of Pani (varying from 5% to 25%) on the chain extended PUs has been reported. The Pani‐filled chain extended PU sheets were characterized by their physico‐mechanical properties such as density, tensile strength, percentage elongation at break and surface hardness. Electrical properties, such as volume and surface conductivity, also have been reported. These results are corroborated with microcrystalline parameters of PU/Pani estimated using wide angle X‐ray scattering (WAXS). Polym. Eng. Sci. 44:772–778, 2004. © 2004 Society of Plastics Engineers.     

Sol-gel synthesis of polyaniline/zirconia composite conducting materials

Polyaniline (Pani) conducting polymer was successfully synthesized by an emulsion polymerization of aniline monomer in the presence of dodecyl benzene sulfonic acid (DBSA). Consequently novel Pani.DBSA/zirconia composites (PDZr) were successfully synthesized by sol-gel technique. Structural and morphological characterization of PDZr composites were carried out using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible spectroscopy (UV–Vis), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Upon incorporating zirconia the resulting composite material showed greater crystallinity. The FT-IR spectrum showed the characteristic peaks of Pani.DBSA shifted to higher wavenumbers. This suggests some interactions between zirconia network and Pani.DBSA polymer chains. TEM micrographs indicate morphological changes upon the formation of PDZr composites. The nanoparticles of Pani.DBSA formed rod-like structures in the resulting composite materials. A higher electrical conductivity was obtained when the PDZr composite was incorporated with 30 % weight of Zr(IV)-n-propoxide. Differential scanning calorimetry (DSC) measurements revealed two distinct glass transition temperature (T_g) for PDZr composite at low percentage of zirconia. Thermogravimetric analysis (TGA) results indicate that the maximum degradation temperature of the PDZr composites increased significantly to 484 °C.     

Blends of styrene butadiene styrene TRI block copolymer/polyaniline-Characterization by WAXS

Electrically conductive blends based on polyaniline-dodecylbenzene sulphonic acid (Pani.DBSA)/styrene-butadiene-styrene (SBS) block copolymer have been prepared by two methods namely melt mixing and polymerization of aniline in the presence of SBS using in situ polymerization method. The influence of composition and synthetic methods on the performance of SBS/Pani blends was established. The obtained SBS/Pani blends have been characterized by mechanical, morphological and electrical properties. A great reduction in volume resistivity values with increase in Pani content was noticed for in situ polymerization method compared to melt mixing method. The microstructural parameters were also computed using Wide Angle X-ray Scattering (WAXS). The results are compared with mechanical and electrical properties.     

Dielectric behavior of natural rubber composites in microwave fields

In this article, we report the preparation of conducting natural rubber (NR) with polyaniline (Pani). NR was made into a conductive material by the compounding of NR with Pani in powder form. NR latex was made into a conductive material by the in situ polymerization of aniline in the presence of NR latex. Different compositions of Pani–NR semi‐interpenetrating networks were prepared, and the dielectric properties of all of the samples were determined in microwave frequencies. The cavity perturbation technique was used for this study. A HP8510 vector network analyzer with a rectangular cavity resonator was used for this study. S bands 2–4 GHz in frequency were used. Thermal studies were also carried out with thermogravimetric analysis and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2682–2686, 2007     

Effect of protonation media on chemically and electrochemically synthesized polyaniline

Polyaniline films have been prepared both chemically and electrochemically using formic (‘Pani‐Formic’), boric (‘Pani‐Boric’) or acetic acid (‘Pani‐Acetic’) as protonation media. Among the three, formic acid seems to be a better protonating medium because it selectively yields the conducting phase of polyaniline. The variation of potential with the amount of oxidizing agent suggests one dimensional growth of polymer chain, which proceeds through a PG/EM mechanism as indicated by spectral data. The Pani‐Boric and Pani‐Acetic acid demonstrate three‐ and four‐step decomposition patterns, respectively, with complete decomposition at about 760 °C. Pani‐Formic acid, in contrast, reveals a three‐step decomposition pattern with 90% weight loss at about 900 °C and shows a tendency to react with the Pt sample holder. The films of polyaniline generated electrochemically also suggest formic acid to be a better protonating medium for achieving a relatively greater fraction of conducting emeraldine salt. However, boric acid produces excellent quality adherent films with very high deposition rate. Morphological features give strong support to this observation. The films of Pani‐Formic and Pani‐Acetic acids show a spongy network and globular morphology, respectively, while Pani‐Boric acid yields an extremely uniform surface coating. Furthermore, cyclic voltammetry reveals different patterns depending upon the formation of different oxidation states and the results are in accordance with optical absorption studies. © 2000 Society of Chemical Industry     

Gas permeability of model polyurethane networks and hybrid organic-inorganic materials: Relations with morphology

Various polyurethane (PU) and hybrid organic-inorganic networks based on isocyanate chemistry were synthesized using a two-stage method. All the networks were amorphous. For PU membranes the morphology and the permeability coefficients of different gases (H₂, N₂, O₂) were a function of the polarity and the chain length of the soft segment and a function of the composition of the networks. The membranes based on the same soft segment chain length and on the same molar composition were structurally nanoheterogeneous systems for the less polar soft segments (α, ω-hydroxy-terminated hydrogenated polybutadiene and a fatty acid oligoester). They were homogeneous for a polycaprolactone type soft segment. The gas diffusion was appreciably hindered in the case of better miscibility between the soft chains and the hard crosslinks. Decreasing the soft segment length decreased the gas permeability coefficient of the network. As the chemical compositions were changed by increasing the soft segment content, an increase in permeability coefficients was observed. The morphology and transport properties of PU networks and hybrid organic-inorganic networks with low inorganic content were compared for the same soft segment content. The similarities observed between the two types of networks led us to conclude that the organic or inorganic nature of the crosslinking agent has no influence on the gas transport properties of these networks. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2579–2587, 1997     

Conductive polyaniline–polychloroprene blends

The electrical conductivity of polychloroprene (CR)/polyaniline (Pani) blends prepared by bulk and solution processes were investigated. Pani doped with HCl (Pani · HCl) and p-toluenesulfonic acid (Pani · TSA) were employed in vulcanized blends obtained by the bulk process. These blends showed an increase in the conductivity only for blend composition of CR/Pani = 50:50 wt %. At this composition, blends with Pani · HCl and Pani · pTSA presented conductivity values of 10⁻⁹ and 10⁻¹⁰ S · cm⁻¹, respectively. CR/Pani · HCl blend films prepared by the solution process displayed surface conductivity values of 10⁻⁴ S · cm⁻¹ with as low as 10–15 wt % of PAni · HCl. Surface analysis of these blends by X-ray photoelectron spectroscopy indicated no traces of the conductive additive. The surface composition was found to be exclusively constituted of CR. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1543–1549, 1998     

Morphology and Thermal Stability of Electrically Conducting Nanocomposites Prepared by Sulfosalicylic Acid Micelles Assisted Polymerization of Aniline in Presence of ZrO2 Nanoparticles

Electrically conductive polyaniline (Pani)/zirconium oxide (ZrO₂) nanocomposites were prepared by in-situ oxidative polymerization of aniline in the presence of sulfosalicylic acid (SSA), HCl and different amounts of ZrO₂ nanoparticles. Pani/ZrO₂ nanocomposites were characterized by Fourier Transform Infra-Red Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The stability of the nanocomposites in terms of DC electrical conductivity retention was also studied in ambient atmosphere by isothermal ageing and cyclic ageing techniques. Pani/ZrO₂ nanocomposites were observed to be more conducting than Pani but showed poorer stability in terms of DC electrical conductivity retention under ambient environmental conditions.     

Polyaniline‐grafted polyurethane coatings for corrosion protection of mild steel surfaces

We report the superior corrosion‐resistant properties of conducting polyurethane networks of polyaniline (PANI), poly‐m‐aminophenol (PmAP), and poly‐o‐anisidine (PoA) coated on mild steel panels. These networks were prepared by blending conducting polyanilines with isocyanate‐containing prepolyurethanes. Free‐standing polyurethane films were obtained after a moisture cure for several days to ensure complete reaction of the excess isocyanate. The films were electrochemically active with conductivity in the range of 10^?2 to 10^?3 S/cm. The solution blends and formed films were characterized by infrared, ultraviolet, thermogravimetric analysis, and differential scanning calorimetry. Electrochemical corrosion studies of the coated films on mild steel panels showed excellent corrosion protection in the following order: PU‐PANI > PU‐PmAP > PU‐PoA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45806.     

Reaction kinetics of irradiation- prepolymerized methyl methacrylate-polyurethane interpenetrating polymer networks by FTIR

The reaction kinetics of irradiation-prepolymerized MMA-PU (polyether) IPNs have been studied by FTIR. The results indicate that the polymerization of each component in the IPN follows its normal distinct reaction mechanism with no mutual interference. Increasing the concentration of TMPTMA (crosslinking agent of PMMA) increased the formation rate of PMMA, while the formation rate of PU networks remained almost the same. Increasing the concentration of TMP (crosslinking agent of PU) increased the formation rate of PU, while the formation rate of PMMA networks decreased. The formation rate of PU was obviously faster than that of PMMA. A theory for the cage effect of the PU network has been proposed.     

聚氨酯接枝聚丙烯酸共聚物网络的合成与性能表征

介绍聚氨酯接枝聚丙烯共聚物网络的合成与性能表征。利用异氰酸酯封端的聚氨酯预聚物同丙烯酸／丙烯酸羟丙酯共聚物反应得到了聚氨酯接枝聚丙烯酸共聚物网络。用利叶变换红外光谱表征了网络的化学组成，用应力－应变实验测试了本聚合物网络的力学性能，用动态粘弹谱以及差示扫描量热法研究了随着ＰＵ与ＰＡ链段比例的改变，该交联体系相结合的变化。     

Preparation, electrochemical characterization and charge–discharge of reticulated vitreous carbon/polyaniline composite electrodes

Polyaniline was electrodeposited onto reticulated vitreous carbon – RVC – in order to obtain a tridimensional composite electrode. Three variations of these electrodes were analysed: a small-anion-doped polyaniline (RVC/Pani), a polyanion-doped polyaniline (RVC/PaniPSS) and a bi-layer type formed by an inner layer of the first electrode and an outer layer of the second one (RVC/Pani/PaniPSS). These composites were characterized by cyclic voltammetry, scanning electronic microscopy and electrochemical impedance spectroscopy. Photomicrographies, voltammetric profiles and impedance data pointed to different morphological and electrochemical characteristics for polyaniline doped with small or large anions, and a mixed behavior for the bi-layer electrodes. Charge–discharge tests for these tridimensional (3D) electrodes, employed as the cathode in lithium batteries, indicated better performance for the RVC/Pani electrode. These RVC composites presented higher specific capacities when compared with those obtained for Pani deposited onto bidimensional substrates.     

Analysis of unsaturated polyester-polyurethane interpenetrating polymer networks. I: Reaction kinetics and viscosity model

The reaction kinetics and viscosity behavior during the reaction injection molding (RIM) process of unsaturated polyester (UPE)-Polyurethane (PU) interpenetrating polymer networks (IPNs) were studied. The interaction between the reactants of the component polymers was reflected in the reaction kinetic model. The intermediate reaction products having a certain conversion level were prepared in order to obtain the conversion dependence of viscosity. The composition dependence of blend viscosity was also evaluated for, the oligomeric mixture.     

PU/EP/PPGDA三元IPN弹性体的结构研究

用红外光谱 (IR)、扫描电子显微镜 (SEM )、X光电子能谱 (XPS)研究了以聚氨酯 (PU)为第一网络的三元IPN聚氨酯 /环氧树酯 /聚丙二醇二丙烯酸酯 (IPNPU/EP/PPGDA)弹性体的互穿特性和形态结构。研究结果表明 ,各元素在三元IPN表面和内部分布不一致 ,表明三种聚合物在IPN中的分布是不均匀的 ,这种差异与IPN组成、组成聚合物间的相容性以及形态结构有密切联系     

Miscibility and properties of semi‐interpenetrating polymer networks based on polyurethane and nitroguar gum

Films from castor oil‐based polyurethane (PU) prepolymer and nitroguar gum (NGG) with different contents (10–70 wt %) were prepared through solution casting method. The networks of PU crosslinked with 1,4‐butanediol were interpenetrated by linear NGG to form semi‐interpenetrating polymer networks (semi‐IPNs) in the blend films. The miscibility, morphology, and properties of the semi‐IPNs coded as PUNG films were investigated with Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, wide‐angle X‐ray diffraction, density measurement, ultraviolet spectroscopy, thermogravimetric analysis, tensile, and solvent‐resistance testing. The results revealed that the semi‐IPNs films have good miscibility over the entire composition ratio of PU to NGG under study. The occurrence of hydrogen‐bonding interaction between PU and NGG played a key role in improvement of the material performance. Compared with the pure PU film, the PUNG films exhibited higher values of tensile strength (11.7–28.4 MPa). Meanwhile, incorporating NGG into the PU networks led to an improvement of thermal stability and better solvent‐resistance of the resulting materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4068–4079, 2007     

Preparation and physical properties of polyurethane modified with poly(4,4′-diphenylsulfone terephthalamide)

Three conventional polyurethane (PU) elastomers were blended physically with various ratios of high molecular weight of poly(4,4′-diphenylsulfone terephthalamide) (PSA) to form 12 PU/PSA polyblends in order to modify their physical properties. Also three new polyurethanes were synthesized with a low-molecular-weight PSA prepolymer as a hydrogen donor for chain extending. From dynamic properties, it showed that both the blends and the new polyurethanes (or polyurethane-ureas) exhibited a glass transition temperature (T_g) below 0°C and had a higher modulus E′ than those of the conventional PU. Based on the analysis of X-ray diffraction of the conventional and the new PU, it was shown that the degree of stress-induced crystallization was dependent on the segmental composition of the soft and hard segments and also the degree of its stretching. On the morphological observation, it was revealed that both the blends and the new polyurethanes were in a dispersed phase structure, although new PU exhibited a better compatible state. For tensile properties, it was found that both tensile strength and elongation of the new polyurethanes were better than those of the blends and conventional PU. © 1994 John Wiley & Sons, Inc.     

Interpenetrating polymer networks based on polyol modified castor oil polyurethane and poly(2‐ethoxyethyl methacrylate): Synthesis,chemical, mechanical,thermal properties,and morphology

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC‐PU) and poly(2‐ethoxyethyl methacrylate) poly(2‐EOEMA) were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate (EGDM) as crosslinker. GC‐PU/poly (2‐EOEMA) interpenetrating polymer networks were obtained by transfer molding. The novel GC‐PU/poly (2‐EOEMA) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents thermal behavior (DSC, TGA) and mechanical behavior, including tensile strength, Young's modulus, shore A hardness, and elongation. The morphological behavior was studied by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1029–1034, 2004     

Conducting polypyrrole‐coated banana fiber composites: Preparation and characterization

In this study, conducting banana fibers (BF) were obtained through in situ oxidative polymerization of pyrrole (Py) on the BF surface using ferric chloride hexahydratate (FeCl₃·6H₂O) as an oxidant. Suitable reaction conditions are outlined for the polymerization of Py: oxidant/monomer molar ratio, Py concentration and polymerization time of 2/1, 0.05 mol.L⁻¹ and 30 min, respectively. Under these conditions, high‐quality conducting fibers containing polyPy and BF (PPy‐BF) were obtained with an electrical resistivity as low as 0.54 Ω.cm. The PPy‐BF was blended with different concentrations of polyurethane (PU) by mixing the two components in a vacuum chamber and then applying compression molding. The electrical resistivity of composites with 25 wt% of PPy‐BF was around 1.8 × 10⁵ Ωcm, which is approximately 10⁸ times lower than that found for pure PU. Moreover, PU/PPy‐BF composites exhibited higher mechanical properties than pure PU and PU/PPy, indicating that these conducting fibers can also be used as reinforcement for polymer matrices. The properties of the PPy‐BF obtained by the method described herein open interesting possibilities for novel applications of electrically conducting fibers, from smart sensors to new conducting fillers that can be incorporated into several polymer matrixes to develop conducting polymer composites with good mechanical properties.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers