Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

A novel self-assembly approach to form tubular poly(diphenylamine) inside the mesoporous silica

MCM-41 materials were synthesized using alkyl(decosane, dodecyl)trimethyl ammonium bromide as structure directing surfactants. X-ray diffraction (XRD) analysis and nitrogen adsorption measurements reveal that the pores are hexagonal with tunable textural properties through the choice of surfactant and experimental condition. Poly(diphenylamine), PDPA was entrapped into the pores of MCM-41 by initial sorption of diphenylamine (DPA, monomer) in a medium (napthalein sulfonic acid) that provides self-assembling of DPA inside the pores and subsequent oxidative of polymerization with peroxydisulphate. Clear presence of an additional peak (around 9-10°) in XRD pattern for the DPA loaded MCM-41 provides evidence for self-assembled structure. Upon polymerization the self-assembly of DPA molecules resulted tubular PDPA inside the pores of MCM-41. PDPA thus formed shows different electronic property than the PDPA prepared by conventional method. XRD and FTIR spectroscopic analysis of PDPA loaded MCM-41 clearly informs that PDPA are entrapped in channels of MCM-41.     

Preparation and characterization of polydiphenylamine/multi‐walled carbon nanotube composites

We describe the synthesis of methane sulfonic acid (MeSA)‐doped poly(diphenylamine) (PDPA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Diphenylamine monomers were adsorbed on to the surface of c‐MWNTs and polymerized to form PDPA/c‐MWNT composites. SEM and TEM images indicated two different types of materials: the thinner fibrous phase and the larger globular phase. The individual fibrous phase had a diameter around 100–130 nm, which should be the carbon nanotubes (diameter 20–30 nm) coated with a PDPA layer. The structure of PDPA/c‐MWNT composites was characterized by FTIR, UV‐visible spectroscopy and X‐ray diffraction patterns. The electrical conductivities of PDPA/c‐MWNT composites were much higher than that of PDPA without c‐MWNTs. Copyright © 2006 Society of Chemical Industry     

聚甲醛/弹性体/纳米碳酸钙复合材料的制备及性能研究

采用双螺杆熔融共混的方法,以4种不同的混合顺序,制备了聚甲醛/热塑性聚氨酯弹性体/纳米碳酸钙（POM/TPU/nano-CaCO3）复合材料。通过力学性能测试、偏光显微镜、差示扫描量热仪、熔体流动速率仪和扫描电子显微镜,考察了nano-CaCO3的用量对POM/TPU(90/10)复合材料力学性能的影响,并探讨了共混方式对复合材料力学性能及微观结构形态的影响。结果表明,4 %的nano-CaCO3与TPU预先混合制成母粒再与POM共混得到的复合材料中POM晶粒发生明显细化,缺口冲击强度高达12.5 kJ/m2,冲击性能较为优异。     

A novel soluble PANI/TPU composite doped with inorganic and organic compound acid

A series of novel soluble and thermoplastic polyurethane/polyaniline (TPU/PANI) composites doped with a compound acid, which was composed of an organic acid (p‐toluene sulfonic acid) and an inorganic acid (phosphoric acid), were successfully prepared by in situ polymerization. The effect of aniline (ANI) content, ratio of organic acid/inorganic acid, and different preparation methods on the conductivity of the TPU/PANI composites were investigated by using conductivity measurement. Lithium bisoxalato borate (LiBOB) was added to the prepared in situ TPU/PANI to coordinate with the ether oxygen groups originating from the soft molecular chains of TPU, and thus the conductivity of the composites was further enhanced. The molecular structure, thermal properties, and morphology of the TPU/PANI composites were studied by UV–visible spectroscopy, differential scanning calorimetry, and scanning electron microscopy, respectively. The results show that the in situ TPU/PANI composites doped with the compound acid can be easily dissolved in normal solvents such as dimethylformamide (DMF) and 1,4‐dioxane. The conductivity of the TPU/PANI composites increases with the increase of the ANI content, in the ANI content range of 0–20 wt %; however, the conductivity of the composites reduces with further increment of ANI content. The conductivity of the TPU/PANI composites prepared by in situ polymerization is about two orders of magnitude higher than that prepared by solution blending method. LiBOB can endow the in situ TPU/PANI composites with an ionic conductivity. The dependence of the conductivity on temperature is in good accordance with the Arrhenius equation in the temperature range of 20–80°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Toughening mechanism of PPS/Sr ferrite composites by TPU elastomer

In order to improve the impact strength of PPS‐based strontium ferrite composite, the thermoplastic polyurethane (TPU) elastomer was added in the composite as a toughening agent. The composites were obtained by melt‐blending PPS, TPU and strontium ferrites in twin‐screw extruder. The crystalline state, thermal property, surface morphology and impact strength of the composites were investigated by using X‐ray diffraction, differential scanning calorimetry, thermoravimetric analysis, scanning electron microscope and izod impact test. The addition of TPU improves impact strength of PPS‐based strontium ferrite composite. When the addition of TPU increases to 11wt %, the impact strength of Sr‐ferrite/PPS/TPU composite is enhanced by 51.44% compared with the sample without TPU addition, and reaches to 5.77 kJ/m². The occurrence of bonding interaction between PPS and TPU, demonstrated by a series of experiments, changes the structure and impact properties of PPS. Based on the experimental results, a possible mechanism is proposed to explain the improvement of Sr‐ferrite/PPS/TPU composites, which is different from the conventional toughening mechanism by the conformation of elastomers and the suppression of microcracks propagation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43564.     

Preparation and characterization of thermally conductive thermoplastic polyurethane/h‐BN nanocomposites

Polyurethane nanocomposites are versatile engineering polymers with unique properties. In this study, nano hexagonal boron nitride containing thermoplastic polyurethane elastomers were prepared via melt blending and hot‐pressing techniques. The nanocomposites were characterized using Fourier transform infrared, differential scanning calorimetry, thermal gravimetric analysis, tensile tests, and thermal conductivity measurements. The surface morphology of the TPU/h‐BN composites was characterized by scanning electron microscopy. The optical properties of the composites were determined by UV transmittance measurements and as the amount of h‐BN increased, optical transparencies decreased dramatically. Nanocomposites displayed higher E‐modulus values and lower elongation at break values than the pure TPU elastomer. Char yields of TPUs increased with increasing h‐BN percentage. Moreover, thermal conductivity of the composite materials improved with the incorporation of h‐BN. POLYM. COMPOS., 35:530–538, 2014. © 2013 Society of Plastics Engineers     

TPU/PTW/GF复合材料力学性能的研究

以乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物(PTW)为相容剂,采用平行同向双螺杆挤出机共混挤出制备了无碱玻璃纤维(GF)增强热塑性聚氨酯弹性体(TPU)复合材料。研究了PTW对GF增强聚酯型TPU和聚醚型TPU复合材料力学性能的影响及其微观形貌特征。结果表明:PTW是GF和TPU的有效相容剂;添加6%PTW的增强TPU复合材料的各项性能较佳;GF含量在20%⁴0%之间时增强效果最为明显;PTW与聚酯型TPU的相容性好于聚醚型TPU;电镜照片显示,复合材料中的GF与基体树脂具有较强的界面作用。     

Preparation of thermoplastic polyurethane/graphene oxide composite scaffolds by thermally induced phase separation

In this study, biomedical thermoplastic polyurethane/graphene oxide (TPU/GO) composite scaffolds were successfully prepared using the thermally induced phase separation (TIPS) technique. The microstructure, morphology, and thermal and mechanical properties of the scaffolds were characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and compression tests. Furthermore, NIH 3T3 fibroblast cell viability on the porous scaffolds was investigated via live/dead fluorescent staining and SEM observation. FTIR and Raman results verified the presence of GO in the composites. SEM images showed that the average pore diameter of the composite scaffolds decreased as the amount of GO increased. Additionally, the surface of the specimens became rougher due to the embedded GO. The compressive modulus of composite specimens was increased by nearly 200% and 300% with the addition of 5% and 10% GO, respectively, as compared with pristine TPU. 3T3 fibroblast culture results showed that GO had no apparent cytotoxicity. However, high loading levels of GO may delay cell proliferation on the specimens. POLYM. COMPOS., 35:1408–1417, 2014. © 2013 Society of Plastics Engineers     

Influence of titanium dioxide on crystallization behavior of an ethylene–propylene copolymer

Crystallization of an ethylene–propylene copolymer (E/P) filled with diverse weight percentages of titanium dioxide (TiO₂) was performed under isothermal and nonisothermal conditions to investigate the influence of the inorganic substance on the nucleation and growth mechanisms of the matrix. The overall and radial crystallization rates of the composite materials were measured using, respectively, differential scanning calorimetry (DSC) and optical microscopy. The nucleation density of E/P spherulites as a function of composition was investigated by scanning electron microscopy (SEM), revealing a nucleating effect of TiO₂. A comparison between the spherulitic texture of specimens showed a higher fineness of the composites relative to the neat matrix, whereas no changes of surface nucleation density were appreciable among composites within the explored compositional range. The thermal behavior is discussed in the light of the enhanced thermal conductivity of polymer composites, which conciliates the crystallization kinetics of the matrix, analyzed using the Avrami equation, to optical and SEM observations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3409–3416, 2003     

Supercritical carbon dioxide assisted preparation of conductive polypyrrole/cellulose diacetate composites

Supercritical carbon dioxide (SC‐CO₂) has been used to assist the preparation of conductive polypyrrole/cellulose diacetate (PPy/CDa) composites by in situ chemical oxidative polymerization. The morphology and conductivity of resulted composites were investigated with scanning electron microscopy and four‐probe method, respectively. With the assistance of strong swelling effect of SC‐CO₂, composite films were obtained with a macroscopically homogeneous structure and conductivity up to 10^?1 S cm^?1 order of magnitude. Increasing the pressure of SC‐CO₂ increased conductivity, while increasing the temperature decreased conductivity. For comparison, PPy/CDa composite was also prepared with conventional oxidative method in aqueous solution. From the viewpoint of conductivity and environmental protection, the SC‐CO₂ method showed its superiority over the conventional one. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4575–4580, 2006     

Morphology and properties of renewable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends with thermoplastic polyurethane

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/thermoplastic polyurethane (PHBV/TPU) composites were prepared by solution blending combined with melt processing in an effort to improve the toughness of PHBV and overcome the coalescence phenomena of TPU at the same time. The compatibility, cross‐section morphology, crystal structure, thermal behaviour, and mechanical properties of composites were investigated. Field emission scanning electron microscopy results showed that no distinct interface was found in composites, uniformly dispersed PHBV/TPU composites were obtained. The incorporation of TPU did not change the basic crystalline structure of PHBV, but decreased its crystallinity. What's more, the integrity of PHBV spherulites structure was destroyed and the radial growth rate of spherulites was inhibited. Differential scanning calorimetry results analyzed by Jeziorny method indicated that the nucleation mode of composites did not change. Besides, when TPU content was up to 40 wt%, the initial degradation temperature of PHBV/TPU composite was increased by 5°C, and the elongation‐at‐break was increased by 225% compared with those of PHBV. POLYM. ENG. SCI., 54:1113–1119, 2014. © 2013 Society of Plastics Engineers     

Development of Multiferroism in PVDF with CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanoparticles

Thin films of some polymer-ceramic nanomultiferroic composites (in 0–3 connectivity) of compositions (1-x) PVDF-xCoFe₂O₄ (x?=?0.05, 0.1, 0.5) have been fabricated through a solution casting route. Based on X-ray diffraction pattern and data, basic crystal structure and unit cell parameters were obtained. The surface morphology of the materials was studied using a scanning electron microscopy (SEM) technique. Structural investigation confirms the presence of a polymeric electro-active β-phase of matrix (PVDF) and nano filler spinel phase of the incorporated nano-ceramics. The observed SEM micrographs confirm that the nanoparticles are well distributed in the PVDF matrix without any agglomeration with a lesser spherulitic microstructure. The flexible nano-composites fabricated with polymer (PVDF) and CoFe₂O₄ provide high permittivity (relative dielectric constant) and low loss tangent. An impedance spectroscopy (IS) technique was employed to study the effect of grain and grain boundary in the resistive properties of the composite materials in terms of electric circuit. The study of AC conductivity as a function of frequency follows Jonscher’s power law. The improved conductivity and dielectric, magnetic, and measured first-order magnetoelectric coefficients suggest some promising applications in the embedded capacitors as well as in multifunctional devices.     

SrTiO3-Filled PTFE Composite Laminates for Microwave Substrate Applications

Strontium titanate (SrTiO₃) filled polytetrafluroethylene (PTFE) substrates were fabricated through sigma mixing (SM), extrusion (E), calendering (C) followed by hotpressing (H) (SMECH) process. The filler dispersion in the polymer matrix and the surface morphology were studied using scanning electron microscopic (SEM) technique. The permittivity (ɛ'_r) and loss tangent (tan δ) of the composites were measured using precision impedance and vector network analyzers. The experimental permittivity of filled composites was compared with theoretically predicted values. Dimensionally stable substrate having a permittivity of 13.1 and a loss tangent of 0.0055 at X-band was prepared in the PTFE/SrTiO₃ composite system.     

Morphology and ionic conductivity of thermoplastic polyurethane electrolytes

Thermoplastic polyurethane (TPU) with a mixture of soft segments [poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG)], denoted TPU‐M, was prepared as an ion‐conducting polymer electrolyte. TPUs with PEG and PTMG as soft segments were also synthesized individually as polymer electrolytes. The changes in the morphology and ion conductivity of the phase‐segregated TPU‐based polymer electrolytes as a function of the lithium perchlorate concentration were determined with differential scanning calorimetry, Fourier transform infrared spectroscopy, alternating‐current impedance, and linear sweep voltammetry measurements. Both solid and gelatinous polymer electrolytes were characterized in this study. The effect of temperature on conductivity was studied. The conductivity changes revealed the combined influence of PTMG and PEG units in TPU‐M. The swelling characteristics in a liquid electrolyte and the dimensional stability were evaluated for the three TPUs. Because of its dimensional stability and ionic conductivity, the TPU system containing both PEG and PTMG as soft segments was found to be more suitable for electrolyte applications. A room‐temperature conductivity of approximately 1 × 10^?4 was found for TPU‐M containing 50 wt % liquid electrolyte. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1154–1167, 2004     

Fabrication,antistatic ability,thermal properties,and morphology of a SPE‐based antistatic HIPS composite

Permanently antistatic composites composed of high impact polystyrene (HIPS) and LiClO₄ doped thermoplastic polyurethane/poly(ethylene oxide) (TPU/PEO) solid‐polymer‐electrolyte (SPE) were successfully prepared in a Haake torque rheometer. The HIPS/SPE composites with different ionic conductivities could be fabricated by a normal thermoplastic processing method instead of the conventional solvent‐based casting technique used in SPE. Studies of the rheological and conductive properties of the composites indicated that the fusion time of the composites increased with the PEO content. The surface resistivity of the composites was below 10¹⁰ ohm sq^?1 orders of magnitude, and able to satisfy the requirement of the antistatic packaging field when the PEO content reached 4 phr. The addition of PEO to the composites was helpful for enhancing the conductivity of the HIPS/SPE composites. Thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), tensile tests, and scanning electron microscope (SEM) were used to investigate the thermal, mechanical properties, and morphology of the composites, respectively. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Mechanical and morphological properties of carbon fiber reinforced–modified epoxy composites

Epoxy, prepared through aminomethyl 3,5,5‐trimethylcyclohexylamine hardening of diglycidylether of bisphenol‐A (DGEBA) prepolymer, toughened with polycarbonate (PC) in different proportions, and reinforced with carbon fiber, was investigated by differential scanning calorimetry, tensile and interlaminar shear strength testing, and scanning electron microscopy (SEM). A single glass transition temperature was found in all compositions of the epoxy/PC blend system. The tensile properties of the blend were found to be better than that of the pure epoxy matrix. They increased with PC content up to 10%, beyond which they decreased. The influence of carbon fiber orientation on the mechanical properties of the composites was studied, where the fiber content was kept constant at 68 wt %. Composites with 45° fiber orientation were found to have very weak mechanical properties, and the mechanical properties of the blend matrix composites were found to be better than those of the pure epoxy matrix composites. The fracture and surface morphologies of the composite samples were characterized by SEM. Good bonding was observed between the fiber and matrix for the blend matrix composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3529–3536, 2006     

Submicron copper‐low‐density polyethylene conducting composites: Structural,electrical, and percolation threshold

Copper‐embedded low‐density polyethylene (LDPE) composites were fabricated using different copper concentrations in the polymer matrix. The copper particles were spherical with a mean particle size between 200 and 300 nm. All the samples were compacted under pressure and melted. The LDPE matrix was analyzed using gel permeation chromatography (GPC) and it did not evidence degradation of the LDPE matrix. The microstructure of the composites was examined with scanning electron microscopy. The electrical conductivity was measured as a function of the copper content, and the composite fabricated with a 10 vol % copper presented a conductivity 15 orders of magnitude higher than that of pure LDPE. The enhancement in conductivity can be explained by means of segregated percolation path theory and the experimental results are in agreement with the theoretical law. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Preparation and heat resistance of hollow glass microbead/silicone rubber composite coating

Hollow glass microbead/silicone rubber composite coatings were prepared to improve the heat-resistance and mechanical properties of silicone rubber-based composites, using CE modified SR as the matrix and HGM as the filler. The microscopic morphology and thermal stability of the composites were characterized by scanning electron microscopy (SEM) and thermogravimetric analyzer (TGA), respectively. The results showed that the thermal stability of the composites increases with the increase of filler content. For the composite sample with a HGM mass content of 16.7%, the initial decomposition temperature (T₅) is 408°C, which is 84°C higher than that of silicone rubber. The low density and high sphericity of HGM make it easier to uniformly disperse in the polymer matrix. In addition, compared to silica, which is commonly used as an inorganic filler, the lower thermal conductivity of HGM is also beneficial for achieving better thermal shielding effect. It is confirmed that the insufficient thermal stability of the polymer matrix above 400°C can be compensated for by the properly dispersed inorganic fillers. Therefore, the thermal stability of the composite is improved by the synergistic effect of modified heat-resistant matrix and inorganic filler.