Effect of oxyfluorination on electromagnetic interference shielding of polypyrrole-coated multi-walled carbon nanotubes

The polypyrrole-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ chemical oxidative polymerization of pyrrole on the surface of MWCNTs for the novel electromagnetic interference (EMI) shielding materials. The oxyfluorination treatment on MWCNTs introduced the hydrophilic functional groups resulting in well distribution and higher interfacial affinity between polypyrrole (PPy) and MWCNTs. The PPy phases formed on MWCNTs were observed by SEM. The thickness of PPy on the surface of MWCNTs decreased as increasing the hydrophilic groups on MWCNTs by the oxyfluorination treatment. The PPy-coated MWCNT composites showed the remarkable increases in permittivity, permeability, and EMI shielding efficiency (SE). The EMI SE of PPy-coated MWCNTs increased up about 28.6 dB mainly based on the absorption mechanism.     

Development of Polypyrrole/Epoxy Composites as Isotropically Conductive Adhesives

As a possible replacement for lead bearing solders, metal filled isotropically conductive adhesives (ICAs) have shown a lot of potential recently. But still they have to come a long way and overcome their limitations like low impact strength and moisture instability. The current paper attempts to address the limitations of these ICAs by using intrinsically conducting polymer as a filler in place of metals. Conducting polymer (CP) polypyrrole (PPy) was incorporated as a filler in an epoxy/anhydride (EP) system and its application as an isotropic conductive adhesive was studied. PPy was synthesized by chemical polymerization using dodecyl-benzene sulphonic acid (DBSA) as dopant. The composites with varying PPy concentrations were studied for curing behavior and thermal degradation properties using DSC and TGA, respectively. The composites show good impact properties and conductivity at very low filler concentrations. SEM observations established that PPy particles were dispersed in the epoxy matrix uniformly. The overall characteristics of these conductive adhesives establish that they can be used as conductive adhesives in the electronics industry.     

5‐Sulfoisophthalic acid monolithium salt doped polypyrrole/multiwalled carbon nanotubes composites for EMI shielding application in X‐band (8.2–12.4 GHz)

This article describes the synthesis and characterization of highly conductive polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites prepared by in situ polymerization of pyrrole using 5‐sulfoisophthalic acid monolithium salt [lithio sulfoisophthalic acid (LiSiPA)] as dopant and ferric chloride as oxidant. Several samples were prepared by varying the amounts of MWCNTs ranging from 1 to 5 wt %. Scanning electron microscope and transmission electron microscope images clearly show a thick coating of PPy on surface of MWCNTs. The electrical conductivity of PPy increased with increasing amount of MWCNTs and maximum conductivity observed was 52 S/cm at a loading of 5 wt % of MWCNTs. Pure PPy prepared under similar conditions had a conductivity of 25 S/cm. Electromagnetic interference (EMI) shielding effectiveness (SE) also showed a similar trend and average EMI shielding of ?108 dB (3 mm) was observed for sample having 5 wt % MWCNT in the frequency range of 8.2–12.4 GHz (X‐band). The light weight and absorption dominated total SE of ?93 to ?108 dB of these composites indicate the usefulness of these materials for microwave shielding. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45370.     

Electrodeposition of polypyrrole on aluminium in aqueous tartaric solution

The electrosynthesis of polypyrrole (PPy) has been achieved on aluminium in aqueous medium of tartaric acid by means of cyclic voltammetry, potentiostatic and galvanostatic techniques. Scanning electron microscopy (SEM) and X-ray microanalysis by energy spectroscopy dispersion (EDS) applying on surfaces show that the PPy coating is developed from the metal surface through the cracks of the initial Al₂O₃ layer.A mechanism involving the participation of the supporting electrolyte and the pyrrole (Py) in distinct active sites was proposed based on the linear sweep voltammetry. It is observed for all applied electrochemical techniques that the pyrrole concentration has to be higher than 0.1 M to allow the polypyrrole electrodeposition in acid medium.Scanning electron microscopy, secondary electrons (SE) and backscattering electrons (BE), shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. Moreover, EDS reveals a good homogeneity and compactness of the film achieved in galvanostatic method. The corrosion results in 3% NaCl medium show that the PPy coating decreases the corrosion behaviour of the aluminium. The bilayer Al₂O₃/PPy shows a capacitor with future applications.     

SEBS/PPy.DBSA blends: Preparation and evaluation of electromechanical and dynamic mechanical properties

In this study, the electromechanical and dynamic mechanical properties of electrically conducting polymer blends were investigated. The blends were comprised poly(styrene‐b‐butylene‐ran‐ethylene‐b‐styrene) (SEBS) containing polypyrrole doped with dodecylbenzenesulfonic acid (PPy.DBSA). The two types of PPy.DBSA (with and without an excess of DBSA) were blended with SEBS through the solution casting method at room temperature. The dynamic mechanical characterization of the SEBS/PPy.DBSA blends demonstrated that the use of PPy.DBSA with and without free DBSA molecules results in different degrees of interaction with the two phases of the SEBS copolymer matrix. The changes in the electrical conductivity of the blends during repeated pressure loading/unloading were investigated. The conducting SEBS/PPy.DBSA polymer blends exhibited an increase in the electrical conductivity on pressure loading and underwent a corresponding decrease on unloading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Soluble conducting polypyrrole doped with DBSA–CSA mixed acid

Soluble conductive polypyrrole (PPy) with room temperature conductivity (2–18 S/cm) has been synthesized by doping polypyrrole with mixed acid containing camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA). The solubility and the room temperature conductivity of PPy doped with mixed acid were measured as a function of component of CSA–DBSA mixed acid, and the structure of PPy was characterized by Fourier transform infrared (FTIR), ultraviolet–visible (UV-vis) spectra, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). PPy doped with DBSA–CSA mixed acid is soluble in m-cresol although PPy doped only by CSA is completely insoluble in any solvent. The solubility of PPy doped with mixed acid increases with an increase in the fraction of DBSA in the mixed acid, while the room temperature conductivity of the PPy increases with increasing CSA molar fraction. The UV-vis spectra and electron spin resonance (ESR) measurements showed that both polaron and bipolaron are the charge carrier in the doped PPy with mixed acid. It was proposed that the contribution of CSA to the solubility of PPy doped with mixed acid is to decrease the interaction among PPy chains due to the large molecular size of CSA, while DBSA contributes to the solubility by its good solvating effect derived from its long alkyl chain. These may be a reason that both the solubility and conductivity of PPy are improved by the presence of CSA compared with those of PPy doped only with DBSA. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 1277–1284, 1998     

Anticorrosion efficiency of zinc-filled epoxy coatings containing conducting polymers and pigments

The dependence of the corrosion-inhibiting properties of zinc-filled organic coatings on the nature of the conducting polymers and conducting pigments added and on the pigment particles’ surface coating with conducting polymer layers were investigated. The following materials were selected to examine the corrosion-inhibiting properties of the conducting polymers: polyaniline phosphate (PANI), polypyrrole (PPy), natural graphite, and carbon nanotubes. Conducting pigment combinations for application in coating materials were formulated by applying pigment volume concentrations (PVC) of 0.3%, 0.5% and 1%, which were completed with Zn dust to obtain pigment volume concentrations/critical pigment volume concentrations (PVC/CPVC) = 0.64. Such conducting pigment/zinc dust combinations represented corrosion inhibitors to be used as ingredients in protective coatings. Solvent-based 2K epoxy resin based coating materials containing the corrosion inhibitors so formulated were prepared to examine their anticorrosion properties. The pigmented coatings were subjected to laboratory corrosion tests in simulated corrosion atmospheres and to standardized mechanical resistance tests. The protective coatings so obtained exhibited a higher efficiency than coating materials containing zinc dust alone. The coating material containing carbon nanotubes at PVC = 1% and the coating material containing graphite coated with polypyrrole (C/PPy) at PVC = 0.5% emerged as the best zinc-filled coating materials with respect to their corrosion-inhibiting efficiency. Treatment with the conducting polymers had a beneficial effect on the coating materials’ mechanical properties.     

Conductive epoxy/amine system containing polyaniline doped with dodecylbenzenesulfonic acid

We developed a conductive epoxy/amine system containing polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA). The curing behaviors of diglycidyl ether of bisphenol A with triethylenetetramine (TETA), PAni.DBSA, and both amine compounds at different concentrations were investigated by differential scanning calorimetry (DSC). Epoxy/TETA systems containing PAni.DBSA presented two distinct exothermic peaks at 90°C due to the cure by TETA as a hardener and at 236°C related to PAni.DBSA as the curing agent. The presence of PAni.DBSA in the systems constituted by epoxy/hardener in stoichiometric proportions resulted in a decrease in the glass‐transition temperature of the epoxy matrix, as indicated by DSC and dielectric analyses. Electrical conductivity was determined in the epoxy/amine networks, with the TETA concentration kept constant and also in stoichiometric proportions of mixed hardener (TETA + PAni.DBSA) to epoxy resin. The last condition resulted in a higher electrical conductivity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4059–4065, 2006     

EMI shielding effectiveness and dielectrical properties of SBS/PAni.DBSA blends: Effect of blend preparation

This work investigates the effect of different preparation routes including mechanical mixing and in situ polymerization of aniline on the electromagnetic interference shielding effectiveness (EMI SE) over the X-band (8–12 GHz) frequency range for polyaniline doped with dodecylbenzene sulfonic acid (PAni.DBSA) filled in styrene–butadiene–styrene triblock copolymer matrix. The dc conductivity and dielectrical properties were also investigated. For all systems, the electrical conductivity, dielectric constant, and EMI SE increased with the increase in the concentration of PAni.DBSA. Blends prepared by the in situ polymerization exhibited higher conductivity and dielectric constant and better EMI SE characteristics than the physical blends with similar amount of PAni.DBSA. EMI SE value as high as −35 dB has been achieved with about 30% of PAni.DBSA prepared by the in situ polymerization. Regarding physical blends, those involving PAni.DBSA prepared by a redoping process displayed better EMI SE. For all systems under consideration, the conductivity and EMI SE bear an exponential relationship that can be represented by a master curve. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚乙二醇接枝改性纳米炭黑对环氧树脂固化过程的影响

采用差示扫描量热法研究了以聚乙二醇(PEG)接枝改性的纳米炭黑(NC)(NC-PEG)为填料对环氧树脂/4,4-二氨基二苯砜非等温固化反应的影响,通过Flynn-Wall-Ozawa法和Malek法确定了固化反应的动力学参数.结果表明:两参数的自催化模型能够很好地描述环氧树脂及其复合材料的固化反应过程,各试样的模型拟合结果与实验数据相吻合.NC-PEG能够促进环氧树脂的固化,使固化活化能降低,其中,NC-PEG用量为3 phr时,活化能最低.     

The effect of dopant on structural, thermal and morphological properties of DBSA-doped polypyrrole

Polypyrrole is prepared with different molar ratios of dodecylbenzene sulfonic acid (DBSA) (0.1, 0.2, 0.3 and 0.4) by in situ chemical polymerization method. The reaction temperature was 0–5 °C for 24 h. The FTIR spectrum confirmed the attachment of sulfonyl group in the pyrrole structure. The intensity of polypyrrole increased with increase in sulfur content. SEM graphs revealed the granular morphology of the doped polymer surface. DBSA has had strong effect on morphology with formation of aggregated particles at higher concentrations. Higher concentration of DBSA-doped PPy shows higher thermal stability. The promotion of electron from ground state to excited state of polypyrrole is confirmed by UV spectroscopic studies. Various sizes in particle distribution of DBSA-doped PPy were analyzed by a particle size analyzer. Solubility of polypyrrole was determined at room temperature. The solubility and quantity of polypyrrole increased with higher dopant concentration. Current–voltage (I–V) characteristics were carried out over the temperature range 313–343 K, which was found to be linear. The conductivity of doped-PPy showed high conductivity at low concentration of dopant while, conductivity decreased with increasing concentration of DBSA. The higher doping level of DBSA was confirmed by elemental analysis.     

AC impedance analysis and EMI shielding effectiveness of conductive SBR composites

Flexible conductive polymer composites were prepared using styrene–butadiene rubber (SBR) as a matrix and conductive carbon black as filler. The filler loading was varied from 10 to 60 phr. The complex AC impedance and electromagnetic interference shielding effectiveness (EMI SE) of the composites were measured at the microwave frequencies of 7.8–12.4 GHz. The effect of variation in filler concentration and measurement frequency on the AC impedance and EMI SE of the composites were investigated. Equivalent circuits describing the conduction behavior of the composites were determined by means of Nyquist plots. The complex electric modulus of the composites was also determined. Increase in the filler loading increased the capacitive nature of the materials. The composites were better defined by a parallel resistor–capacitor circuit in series with a resistor. The EMI SE was found to pass through a maximum with increase in frequency. However, with the increase in filler loading and sample thickness of the material, the EMI SE was found to increase continuously. POLYM. ENG. SCI., 46:1342–1349, 2006. © 2006 Society of Plastics Engineers.     

Microwave dielectric properties and EMI shielding effectiveness of poly(styrene‐b‐styrene‐ butadiene‐styrene) copolymer filled with PAni.Dodecylbenzenesulfonic acid and carbon black

Conducting composites of polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA), carbon black (CB) and poly(styrene‐b‐styrene‐butadiene‐b‐styrene) (STF) as supporting matrix were prepared by in situ polymerization. The influence of components and composition (% w/w) on the electromagnetic properties (dielectric constant ε′ and the dielectric loss ε″) and electromagnetic interference shielding effectiveness (EMI‐SE) of the materials were evaluated with a waveguide, using a microwave network analyzer from 8.2 to 12.4 GHz (X‐band). It was found that CB presence generates adverse effects on PAni.DBSA yield during synthesis, as it can be seen by X‐ray diffraction and TGA analyses. The type of PAni.DBSA formed modifies the composites properties. Dielectric constant, loss factor, and EMI shielding increase with conductive filler loading. Both the fillers, individually and in combination, increase the properties; however, the effect is not additive in nature. POLYM. ENG. SCI., 52:2041–2048, 2012. © 2012 Society of Plastics Engineers     

Electrical properties and EMI shielding characteristics of polypyrrole–nylon 6 composite fabrics

Polypyrrole (PPy) was polymerized both chemically and electrochemically in sequence on nylon 6 woven fabrics, giving rise to polypyrrole–nylon 6 composite fabrics (PPy–N) with a high electric conductivity. The stability of the composite prepared by electrochemical polymerization (ECP) on chemical oxidative polymerization (COP) fabric was better than that of the composite prepared solely by the COP process, since the AQSA dopant was able to strongly interact with the PPy main chain and had a large molecular structure. The temperature dependence of the conductivity of the composites was verified over four heating and cooling cycles. The change in conductivity over these four repeated heating and cooling cycles was affected by the interaction between the thermal stability of the dopant and the rearrangement of the PPy main chain. The electromagnetic interference shielding efficiency (EMI SE) values were in the range 5–40 dB and depended on the conductivity and the layer array sequence of the conductive fabric. The composites with a high conductivity represented reflection‐dominant EMI shielding characteristics, which are typical of the EMI shielding characteristics of metals. However, composites with low conductivity showed absorption‐dominant EMI shielding characteristics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1969–1974, 2003     

超支化聚酯增韧环氧体系固化动力学

用示差扫描量热仪(DSC)对端羟基超支化聚酯增韧环氧树脂体系的固化反应动力学过程进行分析.动态DSC研究表明,在超支化聚酯增韧环氧体系中,H30的使用导致固化反应峰值减小,反应热降低;随着H30的使用量的增大,羟基对环氧/胺反应的催化效果越明显.利用Malek模型计算0 phr和15 phr两个配比的整个固化过程的反应活化能.比较发现,使用H30的体系固化反应表现活化能在整个固化过程中变化较小,比较平缓,放热比较均匀,有利于降低体系的热应力.等温DSC研究表明,未添加H30和添加H30的体系的固化反应均符合自催化模型,添加15 phr H30的体系初期有较好的反应活性,反应级数由2.06增大到2.42,固化反应速率常数提高.     

Anticorrosion properties of smart coating based on polyaniline nanoparticles/epoxy-ester system

In this study, the anticorrosive effect of dodecylbenzenesulfonicacid-doped polyaniline nanoparticles [n-PANI (DBSA)] as a conductive polymer was investigated using electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) techniques. Initially, the n-PANI (DBSA) were successfully synthesized via inverse microemulsion polymerization leading to the spherical nanoparticles with an average diameter less than 30 nm. Two coating systems including 1 wt% n-PANI(DBSA) blended epoxy ester (n-PANI(DBSA)/EPE) and neat epoxy ester (EPE) were coated on the carbon steal substrate. The anticorrosion performance of the prepared coatings was studied using EIS measurement in 3.5% NaCl solution during 77 days. The experimental data was modeled using Zview software according to the appropriate equivalent circuit model. The results clearly showed the better corrosion protection of the n-PANI(DBSA)/EPE coating compared to the EPE coating. This behavior was attributed to the ability of n-PANI(DBSA) in releasing dopant anion when the corrosion process is initiated on the metal substrate emphasizing the smart protection of n-PANI(DBSA)/EPE coating. Accordingly, the released dopant anions along with the iron cations provide a secondary barrier layer, which passivates the substrate.     

Enhancement in electrical conductive property of polypyrrole‐coated cotton fabrics using cationic surfactant

Recently, great efforts have been made to gain highly conductive fabrics for smart textiles and flexible electromagnetic shielding materials. Different from the conventional chemical synthesis method, fibrillar polypyrrole was synthesized on the cotton fabrics via a simple chemical polymerization process with micelles of cationic surfactant (cetyltrimethylammonium bromide, CTAB) as soft template. The modified cotton fabric exhibited excellent electrical conductivity and electromagnetic interference shielding effectiveness due to the formation of fibrillar polypyrrole on the fiber surface. Electrical conductivity of fabric surface were studied by four‐probe resistivity system. The highly conductive fabric with surface conductivity of 5.8 S cm^?1 could be obtained by changing cationic surfactant concentration. The electromagnetic interference shielding effectiveness (EMI SE) of the modified fabrics was evaluated by the vector network analyzer instrument. Compared with the sample without using surfactant, the EMI SE value of PPy‐coated cotton fabrics increased by 28% after using 0.03 M CTAB as soft template. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43601.     

Modification of sisal fiber by in situ coating steam explosion and electromagnetic interference shielding effectiveness of sisal fiber/PP composites

The technology of steam explosion was adopted to modify sisal fiber (SF) material and two different carbon particles, expanded graphite and conductive carbon black (CCB), were in situ coated on the surface of SF during steam explosion process. The DC conductivity and electromagnetic interference shielding effectiveness (SE) of the modified SF/polypropylene (PP) composites were studied and the measurement of electromagnetic interference (EMI) SE was conducted in two frequency ranges of 400–1,000 MHz and 1–18 GHz. The experimental results showed that this novel coating technology could improve the SE of the modified SF/PP composites significantly, which has a strong dependence on the loadings of the expanded graphite modified sisal fiber (SF‐EG) and conductive carbon black modified sisal fiber (SF‐CCB). When the loadings of SF‐EG and SF‐CCB reached 50 wt%, the maximum values of the SE were 33 dB and 51 dB, respectively. For the modified SF/PP composites, the experimental EMI SE values are in good correlation with the theoretical calculation values in far field of electromagnetic radiation. POLYM. COMPOS., 35:1038–1043, 2014. © 2013 Society of Plastics Engineers     

Electrically conductive composites of polyurethane derived from castor oil with polypyrrole‐coated peach palm fibers

Electrically conducting fibers were prepared through in situ oxidative polymerization of pyrrole (Py) in the presence of peach palm fibers (PPF) using iron (III) chloride hexahydrate (FeCl₃·6H₂O) as oxidant. The polypyrrole (PPy) coated PPF displayed a PPy layer on the fibers surface, which was responsible for an electrical conductivity of (2.2 ± 0.3) × 10⁻¹ S cm⁻¹, similar to the neat PPy. Electrically conductive composites were prepared by dispersing various amounts of PPy‐coated PPF in a polyurethane matrix derived from castor oil. The polyurethane/PPy‐coated PPF composites (PU/PPF–PPy) exhibited an electrical conductivity higher than PU/PPy blends with similar filler content. This behavior is attributed to the higher aspect ratio of PPF–PPy when compared with PPy particles, inducing a denser conductive network formation in the PU matrix. Electromagnetic interference shielding effectiveness (EMI SE) value in the X‐band (8.2–12.4 GHz) found for PU/PPF–PPy composites containing 25 wt% of PPF–PPy were in the range −12 dB, which corresponds to 93.2% of attenuation, indicating that these composites are promising candidates for EMI shielding applications. POLYM. COMPOS., 38:2146–2155, 2017. © 2015 Society of Plastics Engineers     

High Performance Organic Coatings of Polypyrrole Embedded with Manganese Iron Oxide Nanoparticles for Corrosion Protection of Conductive Copper Surface

Herein, we report the formation of organic composite coating consists of epoxy (EP) reinforced para toluene sulphonic acid (PTSA) doped polypyrrole (PPy)–manganese iron oxide (MnFe₂O₂) as an efficient corrosion inhibitor for copper substrates. The PTSA doped PPy:MnFe₂O₂ nanocomposite was synthesized via in situ polymerization of PPy in the presence of MnFe₂O₂ nanoparticles. Structural features of the prepared samples were characterized through scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), UV–visible spectroscopy and thermogravimetric analysis (TGA). The PTSA doped PPy:MnFe₂O₂ nanocomposite shows excellent conductivity and improved dielectric performance in comparison to pure PPy. The anti-corrosion performance of this organic composite coating was analyzed through Tafel polarization curves, open circuit potential (OCP), corrosion resistance, impedance spectroscopy and oxygen permeability barrier tests. The nanocomposite coating on copper substrate shows superior corrosion protection efficiency (99%) in comparison to pure epoxy (22%). Adhesion strength of the nanocomposite coating shows significant enhancement due to strong dispersions of MnFe₂O₂ nanoparticles in the host matrix. Owing to its improved conductivity, excellent anti-corrosion performance along with superior mechanical properties, the organic nanocomposite coating reported in this work can potentially be used to protect the conductive copper surfaces from harsh corrosive environments.