Electric conductivity of polymer composites with 7,7,8,8-tetracyanoquinodimethan salts

The electric properties of polymer composites with highly conductive 7,7,8,8-tetracyanoquinodimethan (TCNQ) salts such as quinolinium–TCNQ complex salt (), acridinium–TCNQ complex salt (), and N-methylacridinium–TCNQ complex salt () were studied. Polyacrylonitrile (PAN), poly(N-vinylcarbazole) (PVK), and poly(4-vinylpyridine), (P4VP), etc., were chosen as matrix polymers. The resistivity (ρ) of the was 0.37 Ω cm at the content of 20 wt % in the film. When the content of was increased up to 40 wt%, a phase separation of the needle crystals was observed and the ρ value increased. When was dispersed into PAN or PVK, the separation was also observed and the samples showed low conductivity. The uniform films were obtained in the and systems, but the values of ρ were high because of the degradation of the TCNQ salts. Uniform films with the naked eye were obtained in the and systems, and the values of Ω were 0.37, 1.05, and 3.40 Ω cm, respectively. was stable even when dispersed into P4VP. The properties of the composites were influenced by the combination of the TCNQ salts and the polymers. The uniformity and the stability of the composites were necessary to obtain the high conductive composites.     

Ion transport in copolymers of oligo(oxyethylene) methacrylates with monomers having polar group

Copolymers of oligo(oxyethylene) methacrylates and a series of polar comonomers, i.e. acrylamide, acrylonitrile and maleic anhydride, were synthesized as media for dual- or single-ion conduction, and correlation between polymer structure and properties was established through detailed studies on polymer morphology, mechanical property and the ion transport process. Polar groups in the polymer chain sequence were found to enhance matrix polarity and to retard oligoether crystallization, as well as to raise chain rigidity. Therefore, both novel dual- and single-ion conduction are realized, with a simultaneous improvement in the mechanical properties of polymer materials. An investigation about the effect of matrix polarity on the ion transport process is also carried out, making use of the concepts concerning polymer segmental relaxation. Hence the enhanced matrix polarity is found to contribute to the improvement in ion conduction, mainly through its promotion of salt dissociation. However, at high temperature this facilitation is counteracted due to the “anomalous” temperature-dependence of salt dissociation in the polymer matrix, and the higher the matrix polarity, the more drastic is the drop in carrier number with rising temperature.     

Electrical conducting behaviors in polymeric composites with carbonaceous fillers

Several kinds of polymer composites with carbonaceous fillers such as carbon black (CB), vapor‐grown carbon fiber (CF), and carbon nanotube (CNT) are prepared by a gelation/crystallization process or a melt mixing method. The electrical phenomena, changes of electrical conductivities with different filler's type, filler's concentration and temperatures, and the mechanism of electron transport in these carbon‐filled polymer composites are directly influenced by the geometric grain shape and aggregating morphology of the fillers dispersed in the polymer matrix. For the composites of CB and CF, long‐range macroscopic conduction are governed by the percolation phenomenon, the conduction is behaved through the conductive path formed by the conductors' contacting, and the thermal expansion changes the physical dimensions of the entire electrical network and leads to the changes in the electrical phenomenon. Microscopic conduction between conductive elements is influenced by the tunneling barrier or tunneling voltage, which varies with the temperature change, explaining the apparent observation of the temperature dependence of the composites. In comparison with fillers of CB and CF, the CNT performs unique electric properties for their nonspherical geometry and morphology as a three‐dimensional network (high structures), which has been visually proved by SEM photos in our former research, leading to the percolation threshold lower than 1% in the volume fraction and much less temperature dependence in its composites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1037–1044, 2007     

Semiconducting polymers based on charge-transfer complexes. IV. Electrical properties and structure of polymeric charge-transfer complexes

Model electron donor molecules, 10-methylphenothiazine and 4-(methylthio)anisole, and polymeric electron donors which contained these molecules on the side chains of N-acyl-substituted polyethylenimines, were complexed with the electron acceptors, dichlorodicyanoquinone (DDQ), tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), and tetranitrofluorenone (TNF). The model donors formed 1:1 complexes with all the acceptors except TCNE. The polymeric donors formed amorphous complexes with DDQ, TCNQ, and TCNE. Crystalline complexes were formed with TNF which had low melting points (lower than the model complexes and the pure polymer). This is apparently due to poor lateral packing of the polymer chains. Electrical resistivities were lower for all the polymer complexes than for the corresponding model complexes. Electrical resistivity also decreased with increase in complex crystallinity. In the best case the polymer complex was two hundred times as conducting as the model. The concentration of unpaired electrons measured by EPR was nearly independent of temperature. Most of the electrons seen are trapped and do not participate in conduction. Thermal activation energies for conduction were in the range of 0.5–1.8 eV and were nearly equal for the model and corresponding polymeric complexes. Elongation of polymer complex with TCNQ by rolling produces a decrease in resistivity in the roll direction, although the complex is amorphous. This reinforces the hypothesis that conduction is parallel to the polymer backbone. A polymer–tetranitrofluorenone complex was photoconducting, though the photoconductivity was smaller than the dark conductivity at the level of illumination used. Dember and Seebeck effects indicated that the major carrier in the complex was holes.     

Structure and dielectric properties of a thermoplastic blend containing dispersed metal

In the present work broadband dielectric relaxation spectroscopy measurements were employed to investigate the dielectric properties of polymer composites. A polyethylene/polyoxymethylene (PE/POM) thermoplastic blend was used as a matrix, while the inclusions were iron (Fe) particles. For comparison, the two pure polymers- PE and POM- were used as a matrix, too. In the PE/POM-Fe composites, the polymer matrix is two-phase and the filler particles are localized only in the POM phase, resulting in an ordered distribution of the dispersed filler particles within the blend. In PE-Fe and POM-Fe composites, the filler spatial distribution is random. The behaviour of all the composites studied is described in terms of the percolation theory. The PE/POM-Fe composites, based on the PE/POM blend, demonstrate different electrical behaviour compared to that of POM-Fe and PE-Fe systems. The percolation threshold value of the PE/POM-Fe composites was found much lower than that of the other two systems. The results were related to the microstructure of the composites. A schematic model for the morphology of the composites studied has been proposed. This model explains the peculiar behaviour of the PE/POM-Fe composites by taking into account the ordered distribution of the filler particles in a binary polymer matrix. Optical microscopy photographs confirm this model.     

Physical properties of CdS-poly (vinyl alcohol) nanoconducting composite synthesized by organosol techniques and novel application potential

A nanocomposite of poly (vinyl alcohol) (PVA) reinforced with various contents of CdS was synthesized by organosols reaction with particle size in the range of nanoscale. The influence of CdS content on the network structure of PVA matrix such as particle size distribution, gel fraction (GF), equilibrium water content (EWC), water absorption (WA), extent of filler reinforcement (γ), volume fraction of polymer (V_s) number of elastically effective chains (NEC), and X-ray diffraction (XRD) were investigated. The affine and phantom models for physical crosslinks were used to predict the nature of crosslinks. The thermal behavior of PVA-CdS composites has been studied by differential thermal analysis (DTA), Thermogravimetry (TG) and differential scanning calorimetry (DSC). The dc conductivity of the PVA system reinforced with CdS as a function of concentration and temperature has been presented. The PVA composite exhibits considerably high electronic conductivity which increases linearly with the increase of CdS content. The conduction mechanism in PVA-CdS composites is governing by hopping mechanism. The effects of CdS loading and temperature on the thermal conductivity (λ) and specific heats (C_p) were investigated. The antistatic properties and electromagnetic wave shielding effectiveness (EMI) of PVA-CdS composites has been also investigated. The optical properties such as absorbance and transient photo current under applied voltage of PVA-CdS composites were tested. The mechanical properties of PVA-CdS composites were investigated in details. It is proved that the PVA-CdS composites can be effectively used for linear thermistors, antistatic charge dissipation, EMI in the encapsulation of electronic devices, in woven texturing, optical switch and solar cell fabrication.     

聚酰亚胺／聚N－乙烯吡咯烷酮分子复合物的合成和表征

由原位缩聚制备了刚性高分子聚酰亚胺（ＰＩ）和柔性基体聚Ｎ－乙烯吡咯烷附（ＰＶＰ）的分子复合物，并由实验证明了中间体聚酰胺酸（ＰＡ）和聚乙烯吡咯烷酮大分子之间存在的酸一碱相互作用．这种相互作用促进了混容性，使聚酰亚胺能以分子水平或接近分子水平分散在聚毗咯烷酮的基体之中．聚酰亚胺／聚Ｎ－乙烯吡咯烷团分子复合物的薄膜呈透明性，在整个组成范围内只有一个Ｔｇ，显示单相行为。当ＰＩ含量＜２０％时，ＳＥＭ相片呈现均相形貌，看不到ＰＩ微晶．广角Ｘ－ｒａｙ衍射图表明ＰＩ特征结晶峰消失，和无定形的ＰＶＰ完全混容．当ＰＩ含量＞４０％，ＳＥＭ显示有均匀分布的、棒状ＰＩ微晶存在．通过分子复合，即使ＰＩ含量为１０％，聚Ｎ－乙烯吡咯烷酮不再溶于乙醇，耐热性也有提高．     

Hydrogen-bonded networks in organic conductors: crystal structures and electronic properties of charge-transfer salts of tetracyanoquinodimethane with 4,4'-biimidazolium having multiprotonated States

[structure: see text] Novel hydrogen-bonded charge-transfer salts of TCNQ with mono- and diprotonated 4,4'-biimidazolium were synthesized in order to demonstrate the high potential of the 4,4'-biimidazole system in a molecular conductor from the viewpoint of crystal engineering and electronic modulation. Crystal structure analyses of neutral 4,4'-biimidazole and TCNQ salts revealed the formation of two types of hydrogen-bonding modes of the 4,4'-biimidazole moiety depending on the protonated states. Neutral 4,4'-biimidazole possessed a linear chain mode of hydrogen-bonding to construct two-dimensional network. In the TCNQ salt of monoprotonated 4,4'-biimidazolium, the 4,4'-biimidazole moiety formed a dimer by a complementary mode of hydrogen-bonding. In contrast, the salt of diprotonated 4,4'-biimidazolium showed a double linear chain mode of hydrogen-bonding to construct a three-dimensional network. The formation of two types of hydrogen-bonding modes made the difference in the stacking patterns of TCNQ columns and in their transport properties. The TCNQ salt of diprotonated 4,4'-biimidazolium exhibited high electrical conductivity (sigma(rt) = 1.1 x 10(-1) S cm(-1)).     

Polymerization-induced phase separation as a one-step strategy to self-assemble alkanethiol-stabilized gold nanoparticles inside polystyrene domains dispersed in an epoxy matrix

The rational design of nanoparticle (NP)/polymer composites with advanced functional properties is based on controlling the distribution and self-assembly of NPs in the polymer matrix. In this study we report a new one-step strategy to produce the self-assembly of alkanethiol-stabilized Au NPs in one of the phases generated by polymerization-induced phase separation. The polymerization of a formulation composed of stoichiometric amounts of diglycidylether of bisphenol A (DGEBA) and m-xylylenediamine (mXDA), containing polystyrene (PS) and dodecanethiol-stabilized Au NPs as modifiers, produced the phase separation of PS and Au NPs into microdomains dispersed in the epoxy matrix. A subsequent phase separation and self-assembly of Au NPs took place inside the PS domains leading to an increase in their concentration in a region close to the interface as revealed by TEM images. SAXS spectra showed that NPs self-assembled as colloidal crystals with a body-centered cubic (bcc) structure. By an adequate selection of the amount of PS and the nature of the epoxy precursors, different morphologies of the final blend could be generated. This brings the possibility of controlling the dispersion and self-assembly of NPs in the final material.     

聚酰亚胺／聚N－乙烯吡咯烷酮分子复合物的合成和表征

由原位缩聚制备了刚性高分子聚酰亚胺（ＰＩ）和柔性基体聚Ｎ－乙烯吡咯烷附（ＰＶＰ）的分子复合物，并由实验证明了中间体聚酰胺酸（ＰＡ）和聚乙烯吡咯烷酮大分子之间存在的酸一碱相互作用．这种相互作用促进了混容性，使聚酰亚胺能以分子水平或接近分子水平分散在聚毗咯烷酮的基体之中．聚酰亚胺／聚Ｎ－乙烯吡咯烷团分子复合物的薄膜呈透明性，在整个组成范围内只有一个Ｔｇ，显示单相行为。当ＰＩ含量＜２０％时，ＳＥＭ相片呈现均相形貌，看不到ＰＩ微晶．广角Ｘ－ｒａｙ衍射图表明ＰＩ特征结晶峰消失，和无定形的ＰＶＰ完全混容．当ＰＩ含量＞４０％，ＳＥＭ显示有均匀分布的、棒状ＰＩ微晶存在．通过分子复合，即使ＰＩ含量为１０％，聚Ｎ－乙烯吡咯烷酮不再溶于乙醇，耐热性也有提高．     

MWNTs/HDPE复合体系在太赫兹波段的光电性质

利用太赫兹时域光谱技术和电导测量研究了多壁碳纳米管/高密度聚乙烯(MWNTs/HDPE)复合体系的光电性质. 直流电导率结果表明, 复合体系的逾渗阈值在5%左右; 交流电导率则随频率的变化出现一个拐点, 拐点的位置与颗粒浓度以及导电颗粒的存在状态密切相关. 加入碳纳米管后, 复合体系在太赫兹波段的吸收系数和折射率均有很大的提高. 通过假定在此波段导电颗粒在聚合物中的介电行为类似于偶极子的弛豫, 利用Cole-Cole理论对复合材料的介电性质进行了解释.     

Anisotropic electrical conductivity of drawn elastomeric ionene–TCNQ salts

Elastomeric ionene–TCNQ salts with favorable electrical, mechanical, and processing characteristics were drawn mechanically. The electrical conductivity parallel and perpendicular to the drawing axis was investigated. Correlation between anisotropic conductivity and the change in microstructure was discussed. The resistivity ρ at 25°C of the simple salt (EI-TCNQ₀) and the complex salt (EI-TCNQ_0.5) were on the order of 10⁵ and 10² Ω cm, respectively. In the drawn TCNQ salts, the ρ parallel to the drawing axis increased greatly; on the other hand, the ρ perpendicular to this axis increased slightly or was similar to the ρ of the undrawn TCNQ salts. The anisotropy in the ρ of EI-TCNQ_0.5 between the two directions reached 40 times. The activation energy also increased in the direction parallel to the drawing axis. In the undrawn TCNQ salts, the continuous conduction paths exist isotropically. With drawing, the continuous conduction paths, particularly in the direction parallel to the drawing axis, break or make a structural change. The anisotropic conductivity disappeared with time in EI-TCNQ₀; however, it was present in EI-TCNQ_0.5 even after 200 days under ambient conditions.     

Synthesis and properties of transparent luminescent nanocomposites with surface functionalized semiconductor nanocrystals

5-Amino-1,10-phenanthroline (Aphen) was used as an organic ligand to functionalize CdS nanocrystals (NCs) by a ligand-exchange process. The functional Aphen-CdS NCs have strong luminescent emission at 552 nm and good dispersibility in the polar organic monomers. The Aphen-CdS NCs were dispersed in polymeric monomers to prepare a series of transparent luminescent nanocomposites with excellent thermal stability via in-situ bulk polymerization. The fluorescent properties of the Aphen-CdS NCs were well retained in the polymer matrix. It was found that when the methacrylic acid (MAA) and glycidyl methacrylate (GMA) as the comonomers were introduced into the polymer matrix, the emission peaks of the resultant nanocomposites had a blue shift and the fluorescent intensities also increased due to the interaction between NCs and the polymer matrices. The transparent NCs/polymer nanocomposites with tunable fluorescent emission can be potentially used for the fabrication of optoelectronic devices.     

超声引发无皂乳液聚合制备纳米银/PAAEM复合材料及其表征

在不使用气体保护及乳化剂的条件下,超声辐射引发无皂乳液聚合双原位合成纳米银/聚乙酰乙酸基甲基丙烯酸乙酯(PAAEM)复合材料。并通过XRD、FTIR、TEM、HRTEM、XPS和TG等分析方法对其进行表征。结果表明:纳米银粒子具有面心立方结构和球形或近球形形貌,且较均匀地分散在聚合物基体中;纳米银粒子与基体之间的相互作用是纳米银与基体中乙酰乙酸基的羰基氧原子配位所产生的;而且纳米银粒子对基体PAAEM的热学性能有很大影响。     

Green synthesis of polymer nanofibers and their composites as flame‐retardant materials for polymer nanocomposites

Polyaniline nanofibers and their composites with carbon nanotubes were developed as an effective flame‐retardant material using a facile green method. Polyaniline nanofibers were used as a smart flame‐retardant for acrylonitrile–butadiene–styrene polymer. The polyaniline nanofibers were dispersed in polymer matrix forming well‐dispersed polymer nanocomposites. Effect of polyaniline nanofiber mass ratio on the polymer nanocomposite properties was studied. Polyaniline nanofiber composites with carbon nanotubes were also dispersed in polymer matrix. The thermal stability and flammability properties of the polymer nanocomposites were investigated. The rate of burning of polymer nanocomposites achieved 82.5% reduction (7.32 mm/min) compared with virgin polymer (42.5 mm/min). The reduction in peak heat release rate and total heat release of the polymer nanocomposites containing nanofibers achieved 74 and 34%, respectively. Interestingly, the average mass loss rate was significantly reduced by 58% and the emission of carbon monoxide and carbon dioxide gases were suppressed by 20 and 47%, respectively. The effect of polyaniline nanofibers composites on the flammability of polymer nanocomposites was also studied. Polyaniline nanofibers and their composites were characterized using Fourier transform infrared spectroscopy and transmission and scanning electron microscopy. The dispersion of polyaniline nanofibers in polymer nanocomposites was characterized using transmission electron microscopy. The different polymer nanocomposites were characterized using thermogravimetric analysis, UL94 flame chamber, and cone calorimeter tests. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal and mechanical properties of fluoroaramid-silica nanocomposites

Fluoroaramids have been used as an attractive matrix polymer for composites due to their excellent mechanical and surface properties. Properties of these polymers can be improved further by dispersing silica in these matrices at a nano-scale via the sol–gel process. The role of interfacial interaction on the thermal and mechanical properties in such hybrids has been investigated in the present work. Two types of hybrids have been prepared; one using the aramid matrix with pendant alkoxy groups on the chain and other without. Silica network was developed by addition of tetraethoxysilane and its subsequent hydrolysis and condensation in the polymer matrix. Well dispersed inorganic domains of nanometer scale were obtained in case of matrix with pendant alkoxy groups on the chain, which showed larger increase in the α- and β-relaxation temperatures, storage modulus and thermal stability as compared to the matrix without alkoxy groups. The role of interfacial interaction, and its effect on properties on the fluoroaramid-silica hybrid composites has been discussed.     

Coupled protonic and electronic conduction in the molecular conductor [2-(2-1H-Benzimidazolyl)-1H-benzimidazolium]-TCNQ

A novel molecular based proton-electron mixed conductor, (H3BBIM(+))(TCNQ)(Cl(-))(0.5)(H(2)O) (1), where H3BBIM(+) is 2-(2-1H-benzimidazolyl)-1H-benzimidazolium and TCNQ is 7,7,8,8-tetracyano-p-quinodimethane, was synthesized. The salt exhibited peculiar phase transitions as a result of proton-electron coupling phenomena within the crystal. Salt 1 is composed of a closed-shell H3BBIM(+) cation and an open-shell TCNQ anion radical, and was obtained by electrocrystallization in a buffered CH(3)CN solution. Crystal 1 was constructed from the segregated uniform stacks of H3BBIM(+) and TCNQ. The regular stack of partially electron-transferred TCNQ(-0.5) provided a one-dimensional electron-conducting column. Between the regular H3BBIM(+) columns, a channel-like sequence of holes was formed at the side-by-side space that is filled with disordered Cl(-) ions and H(2)O molecules, and which offer a proton-conducting path. The electrical conductivity at room temperature (10 S cm(-1)) was greater by a magnitude of four than the protonic conductivity (1x10(-3) S cm(-1)). Electronic conduction changed from metallic (T>250 K) to semiconducting (250>T>100 K), then insulating (T<100 K). Protonic conductivity was observed above 200 K. The continuous metal-semiconductor transition at 250 K is caused by the formation of the Cl(-) superstructure, whereas the disappearance of protonic conductivity at 200 K is related to the rearrangement of the [Cl(-)-(H(2)O)(2)] sublattice within the channel. The magnetic susceptibility continuously shifted from Pauli paramagnetism (T>250 K) to the one-dimensional linear Heisenberg antiferromagnetic chain (T<250 K). Lattice dimerization in regular TCNQ columns was confirmed by the appearance of vibrational a(g) mode at low temperatures. The strong localization of conduction electrons on each TCNQ dimer caused a Mott transition at 100 K. The melting and freezing of the [Cl(-)-(H(2)O)(2)] sublattice within the channel was correlated to the conduction electrons on the TCNQ stack and the protonic conductivity.     

Thermal Behavior of Dispersed Vanadium Dioxide Particles in Polyethylene Glycol Matrix Containing Tetraethylammonium Bromide

A study has been made on samples of dispersed vanadium dioxide (VO₂) in a matrix of polyethylene glycol (PEG) doped with a quaternary ammonium salt (QAS), namely tetraethylammonium bromide. It has been established that under the influence of the dopant the heating of a sample up to the temperature of the metal-semiconductor phase transition (MSPT) results in a phase in homogeneity of the sample. On the basis of the results of this study it is possible to conclude that small concentrations of QAS in a PEG matrix can exert a strong effect on the electronic structure of dispersed VO₂ particles. This is accompanied by the appearance of phase heterogeneity of VO₂ which manifests itself in the fact that - with the onset of MSPT with increasing temperature - one portion of the substance passes into the metallic state, and the other remains in the semiconductive state. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nanocellulose reinforced as green agent in polymer matrix composites applications

Owing to their abundance, high strength and stiffness, and low weight and biodegradability, nanocellulose (NC) is regarded as a promising candidate for the preparation of green composites. The high reinforcing effect assigned to the mechanical percolation phenomenon of NC is due to the stiff continuous networks of cellulosic nanoparticles linked via hydrogen bonding. Compared to nanocrystalline cellulose, NC fibers result in more significant improvement to the modulus, stiffness, and strength as aspect ratio NC fiber is higher compared to NC crystal. Indeed, in the case of biopolymer composites, the reinforcement effect of NC is attributed to the NC‐polymer interactions and the reinforcing effect occurring through effective stress transfer at the NC‐polymer interface. The NC‐reinforced composites tend to become more brittle as the concentration of the reinforcing particles increase up to the saturated level, due to the reduction in surface adhesion between filler and matrix. Due to its promising mechanical and structural stability, NC composites have been used widely in many industrial applications such as food packaging, electronic applications, and tissue engineering.     

Molecular composites of polyimide/poly-n-vinylpyrrolidone by in-situ polycondensation

The molecular composites of polyimide (PI) with poly-n-vinylpyrrolidone (PVP) were successfully synthesized by in-situ polycondensation of the rigid polymer in the matrix polymer solution. A strong acid-base interaction between the polyamic acid (the precursor of PI) and the PVP was confirmed experimentally. By this specific interaction the miscibility of PI with PVP was substantially improved. The PI dispersed in the PVP matrix polymer on a molecular level or nearly molecular level.