Properties of Graphene/Waterborne Polyurethane Nanocomposites Cast from Colloidal Dispersion Mixtures

Nanocomposites of waterborne polyurethane (WPU) reinforced with functionalized graphene sheets (FGSs) were effectively prepared by casting from a colloidal dispersion of FGS and WPU, and the morphology and physical properties were examined. The finer aqueous FGS dispersions or WPU with smaller particles yielded nanocomposites with enhanced electrical conductivity and thermal resistance due to finely dispersed FGS. The FGS nucleated the crystallization of the polycaprolactone (PCL) segments in WPU and improved its modulus. However, FGS inhibited crystal growth and deteriorated the tensile properties at high deformation, i.e., tensile strength and elongation at break, because the interaction between FGS and WPU hindered the chain rearrangement of WPU in the nanocomposite.     

In Situ Synthesis and Characterization of Polypyrrole/Graphene Conductive Nanocomposites via Electrochemical Polymerization and Chemical Reduction

Polypyrrole/graphene sheets (PPy/GNs) nanocomposite electrodes were in- situ synthesized via electrochemical polymerization and chemical reduction from pyrrole (Py) and graphene oxide (GO). The surface morphologies of the nanocomposites were observed by scanning electron microscopy (SEM). The SEM results showed graphene sheets (GNs) scattered on the surface of the polypyrrole (PPy), and the morphologies of PPy/GNs nanocomposites manufactured by pulse current (PC-PPy/GNs) or direct current (DC-PPy/GNs) were smoother than that of PC-PPy. The electrochemical capacitance properties of the nanocomposite films were measured by cyclic voltammetry (CV), galvanostatic charge and discharge (GC), and electrochemical impedance spectroscopy (EIS) techniques in 3 mol·L^?1 KCl aqueous solutions. The results indicated that the specific capacitance of the DC-PPy/GNs nanocomposite was 13.5% higher than that of a PC-PPy electrode. Comparison of the electrochemical performance of the nanocomposites indicated that the PC-PPy/GNs nanocomposite had higher specific capacitance and better charging/discharging capability than that of the DC-PPy/GNs nanocomposite. The specific capacitance of the PC-PPy/GNs nanocomposite could reach to 280 F·g^?1 at a scanning rate of 100 mV·s^?1.     

Preparation and Characterization of the Polyaniline Nanocomposites with Electricity/Magnetic Properties

Three kinds of magnetic particle (water-based NiZn ferrite fluid, water-based Fe₃O₄ magnetic fluid, and silicon-oil-based Fe₃O₄ magnetic fluid)/polyaniline nanocomposites were prepared in this study. The samples, after drying and grinding, were characterized by infrared spectrometry (IR), X-ray diffraction (XRD), and UV-vis, scanning electron microscope (SEM); their electromagnetic properties were also measured. The conductivitiy of the resulting water-based NiZn ferrite/polyaniline nanocomposites (WBNiZnFe/PA) was the greatest, reaching 0.094 s/cm, while the conductivitiy for water-based Fe₃O₄ magnetic particle/polyaniline nanocomposites (WBFe₃O₄/PA) was the lowest, reaching only 0.068 s/cm. The saturation magnetization for WBFe₃O₄/PA was the greatest, being 1.5 emu/g, while the saturation magnetization for WBNiZnFe/PA was the lowest, being only 0.8 emu/g. The coercivity of all magnetic particle/polyaniline nanocomposites was about He = 200 Oe.     

Microstructure and Properties of Polypropylene/Clay Nanocomposites

Nanocomposites of polypropylene (PP) containing various contents of Cloisite 15A nanoclay particles were prepared by one-step melt compounding in a twin screw extruder. Tensile and impact properties of the nanocomposite systems were investigated and correlated with their microstructures. The tensile modulus increased with an increase in Cloisite 15A content but the tensile strength, elongation at break, and impact strength were decreased. WAXS and TEM studies showed almost exfoliated structures. There was a decrease in permeability values with an increase in nanoclay content up to 5 wt. %. Exceeding this content of nanoclay had no significant effect on permeation due to the aggregation phenomenon at high concentrations of the nanoparticles. Most of the examined micromechanical models for prediction of the tensile modulus of the nanocomposite were successful despite being based on fiber-shaped fillers. An exfoliated structure of clay within the nanocomposite was assumed for the modeling using a molecular dynamics simulations approach, employing Dreiding, Forcite, and COMPASS force fields, in order to investigate the best one for a successful estimation of elastic modulus. Relative to the experimental modulus values of the nanocomposites, which were around 1100–1200 MPa, the COMPASS force field had the best correlation with the values with a slight departure of about 10%.     

Thermal Stability and Degradation Kinetics of Poly(Methyl Methacrylate)/Sepiolite Nanocomposites by Direct Melt Compounding

Poly(methyl methacrylate) (PMMA) nanocomposites based on sepiolite modified with trimethyl hydrogenated tallow amine by an adsorption process were prepared by melt compounding using a corotating twin screw extruder. The morphology and dispersion of sepiolite in the PMMA were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal stability and the activation energies were investigated by thermogravimetric analysis/differential thermogravimetric (TGA/DTG). The XRD and TEM results show that the sepiolite was dispersed homogeneously in the PMMA matrix at a nanometer scale. The TGA analysis revealed that the addition of sepiolite improved the thermal stability of PMMA. The apparent activation energies were calculated by the method of Flynn–Wall–Ozawa in nitrogen at four different heating rates, showing that sepiolite increased the apparent activation energies by about 20 kJ/mol within the degree of conversion (α) of 0.35–0.9, as compared with the reference PMMA sample.     

Preparation and Characterization of Silicon-containing Polyarylacetylene/montmorilloite Nanocomposites

Dimethylphenylpropargyl ammonium bromide (DMPPAB) was synthesized and used to modify pristine montmorillonite (MMT) by a cation exchange process. The organically modified montmorillonite (OMMT) was verified and used to mix with a silicon-containing polyarylacetylene (PSA) as well as MMT. The PSA/MMT and PSA/OMMT nanocomposites were prepared by solution under sonication and melting intercalation processes, respectively, and then cured by a step heating process. The thermal and flexural properties of the cured PSA and nanocomposites were studied by thermogravimetric and dynamic mechanical analysis. The results showed that the intercalation of DMPPAB into the MMT galleries made the d-spacing enlarge. During PSA curing, the cure heat of PSA caused the MMT and OMMT to delaminate and exfoliate in the PSA matrix. The glass transition temperature of the cured PSA and nanocomposites were higher than 500?°C. The inner acetylenic groups in the PSA resin could further crosslink above 300?°C. The temperature at 5% mass loss of the cured PSA decreased by 4.6% with 3% mass fraction of OMMT loading, and the char yield of the cured PSA changed only slightly. The flexural strength of the cured PSA was augmented with addition of MMT or OMMT, but the flexural modulus of the cured PSA decreased slightly. The flexural strength of the cured nanocomposite increased from 20.1?MPa to 30.1?MPa when 3% mass fraction of OMMT was added into the PSA matrix.     

Thermal,Mechanical, and Rheological Characterization of Polylactic Acid/Halloysite Nanotube Nanocomposites

Halloysite nanotube (HNT) clay and biodegradable polylactic acid (PLA) nanocomposites were fabricated by a melt-blending method with five different clay levels (1, 3, 5, 7, and 9 wt%). The effect of HNT loading on the thermal and mechanical properties of the PLA/HNT nanocomposites was examined by thermogravimetric analysis and universal tensile testing, respectively. Morphological characteristics were investigated by transmission electron microscopy. The composites' melt rheological characteristic analyses were conducted using a rotational rheometer in both steady-shear and oscillatory dynamic testing modes. The data were found to be well-analyzed using the Carreau model, Cox–Merz rule, modified Cole–Cole plot, and van Gurp–Palmen plot.     

Preparation and Rheological Properties of Functionalized Multiwalled Carbon Nanotube/Waterborne Polyurethane Nanocomposites

Waterborne polyurethane (WBPU) was synthesized by a polyaddition reaction with toluene diisocyanate (TDI), polytetramethylene ether glycol (PTMEG), dimethylol propionic acid (DMPA), and triethylamine (TEA). Aqueous polyurethane dispersions with three different weight fractions, 30, 40, and 50 wt%, were prepared. All the dispersions made with these concentrations showed Newtonian viscosity behavior. Multiwalled carbon nanotubes (CNTs) were functionalized using a mixture of sulfuric and nitric acid at a ratio of 3:1 and added to these dispersions in two different loads of 0.1 and 0.5 wt%. Ultraviolet visible spectrometry (UV/Vis) spectroscopy proved the formation of stable suspensions following ultrasonic agitation. The rheology of these suspensions was characterized using dynamic and steady-state measurements. The higher amount of CNT in the suspension imparted non-Newtonian and complex viscoelastic behavior. This was attributed to a physical network formed due to the presence of the functionalized CNTs. The Cox-Merz rule was not observed for these suspensions.     

Rheological and Mechanical Characterization of Multi-Walled Carbon Nanotubes/Polypropylene Nanocomposites

The rheology and morphology of multi-walled carbon nanotube (MWNT)/polypropylene (PP) nanocomposites prepared via melt blending was investigated. The minor phase content of MWNT varied between 0.25 and 8 wt%. From morphological studies using a scanning electron microscopy technique a good dispersion of carbon nanotubes in the PP matrix was observed. The rheological studies were performed by a capillary rheometer, and mechanical properties of the nanocomposites were studied using a tensile and flexural tester. Both PP and its nanocomposites showed non-Newtonian behavior. At low shear rates the addition of MWNT content causes an increase in viscosity; however, viscosity is less sensitive to addition of MWNT content at higher shear rates. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. From this calculation it was concluded that the temperature sensitivity of nanocomposites was increased by increasing of nanotube content. An increase in tensile and flexural moduli and Izod impact strength was also observed by increasing the MWNT content. From rheological and mechanical tests it was concluded that the mechanical and rheological percolation threshold is at 1.5 wt%.     

Structure and Mechanical Properties of 50/50 NR/SBR Blend/Pristine Clay Nanocomposites

A blend/clay nanocomposites of 50/50 (wt%) NR/SBR was prepared via mixing the latex of a 50/50 NR/SBR blend with an aqueous clay dispersion and co‐coagulating the mixture. The structure of the nanocomposite was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Nanocomposites containing less than 10 phr clay showed a fully exfoliated structure. After increasing the clay content to 10 phr, both nonexfoliated (stacked layers) and exfoliated structures were observed in the nanocomposites. The results of mechanical tests showed that the nanocomposites presented better mechanical properties than clay‐free NR/SBR blend vulcanizate. Furthermore, tensile strength, tensile strain at break, and hardness (shore A) increased with increasing clay content, up to 6 phr, and then remained almost constant.     

Preparation and Characterization of Linear Low Density Polyethylene/Carbon Nanotube Nanocomposites

Linear low‐density polyethylene (LLDPE)/multiwalled carbon nanotube (MWNT) nanocomposites were prepared via melt blending. The morphology and degree of dispersion of nanotubes in the polyethylene matrix were investigated using scanning electron microscopy (SEM). Both individual and agglomerates of MWNTs were evident. The rheological behavior and mechanical and electrical properties of the nanocomposites were studied using a capillary rheometer, tensile tester, and Tera ohm‐meter, respectively. Both polyethylene and its nanocomposites showed non‐Newtonian behavior in almost the whole range of shear rate. Addition of carbon nanotubes increased shear stress and shear viscosity. It was also found that the materials experience a fluid‐solid transition below 1 wt% MWNT. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. With increasing nanotube content, the activation energy of flow increases. A decrease of about 7 orders of magnitude was obtained in surface and volume resistivity upon addition of 5 wt% MWNT. In addition, a difference between electrical and rheological percolation thresholds was observed. The results confirm the expected nucleant effect of nanotubes on the crystallization process of polyethylene. A slight increase in Young's modulus was also observed with increasing MWNT content.     

Size-Dependent HCl Generation of PVC/SiO2 Micro- and Nanocomposites

In this study HCl generation of polyvinyl (chloride) (PVC)/SiO₂ composites during its combustion was investigated. SiO₂ with different particle sizes were used as HCl absorbers and their HCl uptake ability results were compared to that of CaCO₃. It was found that the amount of released HCl gas during PVC combustion decreased in the presence of SiO₂. The HCl uptake ability of SiO₂ improved with decreasing of its particle size. Although thermogravimetric analysis (TGA) results showed that SiO₂ particles decreased the first thermal degradation temperature (T _onset) of PVC by initiating dehydrochlorination of PVC at lower temperatures, SiO₂ particles had more effective HCl uptaking ability than that of CaCO₃. Scanning electron microscopy (SEM) micrographs showed that some aggregates whose size was less than 100 nm were formed when Si-25 nm was used as filler. When SiO₂ with micron size was added to PVC as filler, more uniform and better distribution of the SiO₂ on the surface was observed.     

Microstructure and Chemical States of Hydroxyapatite/silk Fibroin Nanocomposites Synthesized via A Wet-mechanochemical Route

Hydroxyapaptite (HAp)/silk fibroin (SF) nanocomposites were prepared via a wet-mechanochemical route at room temperature. The results reveal that the inorganic phase in the composites is carbonate-substituted HAp containing 2.9–3.1 wt% of carbonate ions. The primary HAp crystals are rod-like in shape with a typical size of 20–30nm in length and 8–10nm in width, and lattice parameters a = 9.423, c = 6.888. The self-assembled HAp crystals along their c-axes aggregate into bundles, which are connected with SF fibrils. Consequently, a three-dimensional porous network is formed in the composite, which is beneficial to inducing new bone formation in practical implantation.     

Steady Shear Rheological Behavior,Mechanical Properties,and Morphology of the Polypropylene/Carbon Nanotube Nanocomposites

Nanocomposites based on polypropylene (PP) and multiwall carbon nanotubes (MWNT) have been prepared through melt blending. Scanning electron microscopy (SEM) observations indicate that nanotubes were dispersed almost homogeneously throughout the matrix; however, some aggregates were also observed at high nanotubes loading. Rheological studies showed that at low shear rates, there is an increase in steady shear viscosity and shear stress of samples with increasing of nanotubes concentration. However, at high shear rates nanocomposites behave like pure PP. The activation energy of flow showed an increasing trend and has a maximum at 1wt% MWNT content. It was found that incorporation of nanotubes causes a remarkable decrease in surface and volume resistivity values of the polymeric matrix. The presence of CNTs improved the tensile and flexural properties of the polymeric matrix.     

聚氨酯改性TDE-85/ MeTHPA树脂的固化反应机理及动力学研究

以聚醚二元醇、甲苯二异氰酸酯为原料,合成了聚醚型聚氨酯预聚体(PUP)。采用该预聚体、扩链剂1,4-丁二醇、交联剂三羟甲基丙烷对TDE-85/甲基四氢邻苯二甲酸酐（MeTHPA)环氧树脂体系进行改性,通过示差扫描量热法与红外光谱法分析,探讨了聚氨酯(PU)改性环氧树脂体系固化反应机理及固化反应动力学特征。固化反应机理研究表明,TDE-85与MeTHPA之间的固化反应形成环氧聚合物网络Ⅰ,1,4-丁二醇及三羟甲基丙烷同PUP进行了扩链、交联反应形成了PU聚合物Ⅱ。异氰酸酯基同环氧基反应,使得聚合物Ⅰ与聚合物Ⅱ形成了接枝化学键。固化反应动力学研究表明,PU的加入可明显降低环氧树脂固化反应的表观活化能,活化能由TDE-85/MeTHPA树脂体系时的83.14 kJ/mol降至PU改性后的67.91 kJ/mol。     

Synthesis and Properties of Amine-Cured Epoxy/Organophilic Layered Silicate Nanocomposites

Epoxy-layered silicate composites have been prepared by dispersing an organically modified montmorillonite (Nanofil 919) in an epoxy resin and curing in the presence of an aromatic hardener. Dispersion of the layered silicate within the epoxy matrix was verified using X-ray diffraction and transmission electron microscopy revealing that interaction improves upon organic silicate modification. Flexural properties and toughness increase with the organic silicate loading whereas glass transition temperature decreases and thermal stability remains practically unmodified.     

Rheology,Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

Nylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.     

Synthesis and Non-isothermal Crystallization Behavior of PET/Surface-treated TiO 2 Nanocomposites

Poly(ethylene terephthalate) (PET)/TiO ₂ nanocomposites were prepared by melt-blending PET and surface-treated TiO ₂ . The crystallization behavior and the non-isothermal crystallization kinetics of these composites were investigated by differential scanning calorimetry (DSC). Jeziorny and Mo's methods were applied to describe the kinetics of the non-isothermal crystallization process. It was found that the PET matrix with incorporated surface-treated TiO ₂ particles has lower crystallization temperature and melting point than that with incorporated pure nano-TiO ₂ particles. Unlike plain TiO ₂ , surface-treated TiO ₂ particles showed less effect on the degree of crystallization of the PET matrix.     

ZrN-ZrB2纳米复合材料的高压制备及性能表征

 以金属锆粉（Zr）和六方氮化硼粉（h-BN）为原料,结合高能球磨和高温高压合成技术,制备出了ZrN-ZrB₂纳米复合材料。利用X射线衍射、透射电镜和拉曼光谱等测试手段,对材料的结构和合成规律进行了研究。结果表明,高能球磨过程中只合成出了ZrN_x,没有出现ZrB₂,从N、B原子与Zr进行固态反应的热力学和动力学方面分析了原因。利用Zr与BN粉球磨10 h后的混料,在压力为5 GPa、温度为1 300 ℃的条件下,制备出了具有高致密度的ZrN-ZrB₂纳米复合材料。其维氏显微硬度（17 GPa）、热膨胀系数（7.57×10^-6 ℃^-1）和电阻率-温度系数（8.846×10^-4 ℃^-1）等材料参数的测量结果表明,ZrN-ZrB₂复合材料是一种集优良的力学、热学和电学性能于一体的纳米复合材料。     

新型C60衍生物／Ag复合纳米材料的制备及光谱性质

利用1,3-偶极环加成反应合成了联吡啶基C60单加成衍生物N-甲基-2-[4′-(4″-甲基-2′,2″-联吡啶基)]-3,4-C60吡咯烷(C60BPY),并用NaBH4还原法和银溶胶直接组装法制备了C60BPY/Ag复合纳米结构。透射电子显微镜(TEM)表明,两种复合纳米结构的粒子粒径分别在30~45nm和40~55nm之间,粒子形状较规则,且分散性较好。在复合纳米结构形成过程中,C60BPY分子有效地控制了银粒子的生长和团聚,起到了很好的稳定和分散作用。紫外-可见吸收光谱中,两种复合纳米结构分别在430和490nm处出现了银纳米粒子的表面等离子体共振吸收峰,说明随着粒径的增大,吸收峰发生了红移。荧光发射光谱显示,C60BPY/Ag复合纳米体系猝灭了C60BPY在720和805nm处的发射峰,并对其机理进行了探讨。这种复合纳米体系有望在光电器件、传感器及催化领域有潜在的应用前景。