Synthesis of hierarchical nanohybrid CNT@Ni-PS and its applications in enhancing the tribological,curing and thermal properties of epoxy nanocomposites

Poor interfacial adhesion and dispersity severely obstruct the continued development of carbon nanotube (CNT)-reinforced epoxy (EP) for potential applications. Herein, hierarchical CNT nanohybrids using nickel phyllosilicate (Ni-PS) as surface decorations (CNT@Ni-PS) were synthesized, and the nanocomposites derived from varied mass fractions of EP and CNT@Ni-PS were prepared. The morphological structures, tribological performances, curing behaviors and thermal properties of EP/CNT@Ni-PS nanocomposites were carefully investigated. Results show that hierarchical CNT nanohybrids with homogeneous dispersion and well-bonded interfacial adhesion in the matrix are successfully obtained, presenting significantly improved thermal and tribological properties. Moreover, analysis on cure kinetics proves the excellent promotion of CNT@Ni-PS on the non-isothermal curing process, lowering the curing energy barrier steadily.     

Nickel-based metal−organic framework-derived whisker-shaped nickel phyllosilicate toward efficiently enhanced mechanical,flammable and tribological properties of epoxy nanocomposites

Metal−organic framework-derived materials have attracted significant attention in the applications of functional materials. In this work, the rod-like nickel-based metal−organic frameworks were first synthesized and subsequently employed as the hard templates and nickel sources to prepare the whisker-shaped nickel phyllosilicate using a facile hydrothermal technology. Then, the nickel phyllosilicate whiskers were evaluated to enhance the mechanical, thermal, flammable, and tribological properties of epoxy resin. The results show that adequate nickel phyllosilicate whiskers can disperse well in the matrix, improving the tensile strength and elastic modulus by 13.6% and 56.4%, respectively. Although the addition of nickel phyllosilicate whiskers could not obtain any UL-94 ratings, it enhanced the difficulty in burning the resulted epoxy resin nanocomposites and considerably enhanced thermal stabilities. Additionally, it was demonstrated that such nickel phyllosilicate whiskers preferred to improve the wear resistance instead of the antifriction feature. Moreover, the wear rate of epoxy resin nanocomposites was reduced significantly by 80% for pure epoxy resin by adding 1 phr whiskers. The as-prepared nickel phyllosilicate whiskers proved to be promising reinforcements in preparing of high-performance epoxy resin nanocomposites.     

Effect of oxygen functional groups of reduced graphene oxide on the mechanical and thermal properties of polypropylene nanocomposites

Reduced graphene oxide (rGO) with various surface structures was prepared by reducing graphene oxide (GO) with hydrazine hydrate (N₂H₄), sodium borohydride (NaBH₄) and l ‐ascorbic acid, respectively. The resulting rGO were used to fabricate rGO/polypropylene (PP) nanocomposites by a melt‐blending method. The surface structure of rGO as well as multifunctional properties of rGO/PP nanocomposites were thoroughly investigated. It was shown that rGO with highest C/O ratio could be obtained by reducing GO with N₂H₄. The crystallization behaviors, tensile strength, thermal conductivity and thermal stability of rGO/PP nanocomposites were significantly improved with the increase of C/O ratio of rGO. For example, with only 1 phr (parts per hundred PP) rGO reduced by N₂H₄, the degree of crystallinity, tensile strength, maximum heat decomposition temperature and thermal conductivity of PP nanocomposite were increased by 6.2%, 20.5%, 48.0 °C and 54.5%, respectively, compared with those of pure PP. Moreover, the thermal degradation kinetics indicated that the decomposition activation energy of rGO/PP nanocomposites could be enhanced by adding rGO with higher C/O ratio. © 2018 Society of Chemical Industry     

含氟环氧树脂的合成与性能研究

采用十二氟庚醇与双酚A环氧树脂接枝合成了侧链含氟环氧树脂。采用了力学性能测试、红外光谱(FTIR)、X-射线光电子能谱(XPS)、动态热机械分析(DMTA)及交流阻抗分析(EIS)研究了含氟环氧树脂固化物的力学性能、表面性能及电化学性能等。结果表明,含氟环氧树脂固化后氟元素在表面富集,其断裂延伸率和冲击强度较双酚A环氧树脂分别提高41%和26.8%,交流阻抗提高2个数量级以上。含氟环氧树脂的韧性和电性能显著提高。     

Investigation of thermal behaviour and mechanical property of the functionalised graphene oxide/epoxy resin nanocomposites

ABSTRACT

Graphite oxide (GO) and functionalised graphite oxide (FGO) were successfully prepared with -NH₂-terminated GO in the paper, and their chemical structures were characterised with Fourier transform infrared (FTIR), Energy-Dispersive X-ray Spectroscopy (EDS), UV spectrum analysis and XRD, their microstructures were researched by a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and their thermal properties were characterised by TG. The result showed the carbon residue of FGO was 82.1% and the residual char of GO was 48%, the composite materials were prepared with curing for epoxy resin. The thermal stability, mechanical properties, and morphology after impacting tests of composite materials were investigated using thermogravimetric analysis, tensile and charpy impact tests and SEM. The result showed when the 0.2% FGO was filled into the epoxy, the tensile strength was 55.4?MPa, the impact strength was 17.3?KJ/m², the flexural strength was 82?MPa, and the flexural modulus was 2760?MPa. The mechanical properties of composite materials were higher than those of pure epoxy and improved the strength and toughness of epoxy nanocomposites.     

Synthesis of a novel azaphosphorine flame retardant and its application in epoxy resins

A novel P? C? N bond containing azaphosphorine, 5‐(4‐hydroxy)anilinomethyl‐1,3‐di(4‐hydroxy)phenyl‐1,3,5‐diazaphosphorinane (ADDPP‐OH), which could be used as both a cocuring agent and a flame‐retarding agent for epoxy resins (EPs), was synthesized from tetrakis(hydroxymethyl)phosphonium sulfate and characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, ³¹P‐NMR, and so on. Compared with the pure EP, the ADDPP‐OH–EP composites showed increased decomposition temperatures and char yields. When the content of ADDPP‐OH was 10 wt %, the cured EP composite possessed a limiting oxygen index value of 33.7% and passed the V‐0 rating of the UL‐94 test. The mechanical properties of the ADDPP‐OH–EP composites was improved because of the increased crosslinking density. In addition, the morphology of the residual char indicated an intumescent and multiporous structure in the inner space and a compact and continual appearance in the outer layer; this was important in preventing the materials from burning further. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45721.     

Synthesis of aluminum ethylphenylphosphinate flame retardant and its application in epoxy resin

A novel flame retardant additive, aluminum ethylphenylphosphinate (AEPP), was synthesized from diethyl phenylphosphonite and aluminum chloride hexahydrate, and characterized by FTIR, ¹H NMR, and ³¹P NMR. AEPP was added into diglycidyl ether of bisphenol A epoxy resin (EP) cured by bisphenol A‐formaldehyde novolac resin. The flame retardancy of the cured EP was investigated by limited oxygen index, UL 94 test, and cone calorimeter test. The results revealed that the EP composite containing 15% AEPP had a limited oxygen index value of 28.2% with a UL 94 V‐0 rating. The incorporation of AEPP effectively decreased the peak heat release rate and the total heat release in cone calorimeter test analysis. Scanning electron microscopy results showed that the introduction of AEPP benefited to the formation of a smooth and continuous char layer during combustion of the flame retarded EP. The thermogravimetric analysis results indicated that the incorporation of AEPP promoted the initial decomposition of EP matrix, but AEPP/EP composites had a higher char yield at high temperatures. Moreover, the flexural properties of the flame retarded EP composites were studied.     

石墨烯/聚合物复合材料的研究进展

介绍了石墨烯的制备与改性方法,概述了石墨烯/聚合物复合材料的制备工艺,主要有熔融共混法、原位聚合法、溶液混合法及乳液混合法,并总结了石墨烯对聚合物导电性能、导热性能、耐热性能、物理机械性能和气体阻隔性能的影响.     

Synthesis of imidazolium salts and their application in epoxy montmorillonite nanocomposites

Considerable research has been conducted in improving the performance characteristics of nanocomposites, however, relatively few attempts have been made to address the thermal stability of nanocomposites. An attempt is being made to improve the thermal properties of nanocomposites by synthesizing imidazolium salts from 2-methyl imidazole and ion exchanging the salts with clay minerals. This study focuses on the role of the chemistry of imidazolium salt(s) used in functionalizing clay and processing conditions in the formulation of epoxy nanocomposites. The nanodispersion of clay in an epoxy matrix is evaluated qualitatively by X-ray diffraction (XRD), transmission electronic microscopy (TEM), and laser scanning confocal microscopy (LSCM). We demonstrate the use of LCSM for quantitative image analysis and to study the dispersion of clay layers, tagged with a fluorescent dye in the epoxy matrix. XRD and TEM results reveal that the hand mixed nanocomposite has tactoid morphology, while ultrasonicated organoclay (without hydroxyl group) epoxy nanocomposite exhibits a mixed morphology, and an ultrasonicated organoclay (with hydroxyl group) epoxy nanocomposite had well dispersed clay distribution in the epoxy matrix. Results from the three complimentary techniques enable the characterization of the clay platelets over several length scales ranging from the micrometer to the nanometer scale.     

A simple hydrothermal synthesis of nickel hydroxide-ordered mesoporous carbons nanocomposites and its electrocatalytic application

A simple hydrothermal synthesis of nickel hydroxide-ordered mesoporous carbons nanocomposites (Ni(OH)₂-OMCs) is proposed for the first time. The characterization of the new material shows that, after anchoring Ni(OH)₂ nanoparticles on the mesoporous, ordered mesostructure of the nanocomposites remain intact and Ni(OH)₂ is electrochemically accessible. The performance of Ni(OH)₂-OMCs is compared to OMCs and the properties of the new material are found to be improved. A sensor for sensitive detection of underivatized glycine has been developed based on Ni(OH)₂-OMCs modified glass carbon (Ni(OH)₂-OMCs/GC) electrode. The linear response of glycine measurement was up to about 3.2 mM with a high sensitivity of 10.5 μA mM⁻¹ for the Ni(OH)₂-OMCs/GC electrode. The detection limits was estimated to be 0.26 μM (S/N = 3). Then ethanol was selected as another marked molecule, a nonenzymatic amperometric sensor of ethanol based on the Ni(OH)₂-OMCs nanocomposites is also constructed. The linear response of ethanol measurement was up to about 80 mM with a sensitivity of 0.65 μA mM⁻¹. The detection limits was estimated to be 4.77 μM (S/N = 3).     

Mussel-inspired synthesis of silver nanoparticles as fillers for preparing waterborne polyurethane/Ag nanocomposites with excellent mechanical and antibacterial properties

Silver nanoparticles (AgNPs) were synthesized by a facile, mild and green method using dopamine as a reducing and stabilizing agent and were introduced to waterborne polyurethane (WPU) via an in situ emulsification method to prepare antibacterial nanocomposite films. The formation of AgNPs was characterized by UV–visible spectroscopy and XRD. The dispersion of AgNPs was confirmed by TEM and the thermal stability of WPU/Ag nanocomposites was confirmed by TGA. The results showed that AgNPs were uniformly dispersed in the WPU matrix. The introduction of AgNPs significantly improved the thermal stability of WPU films. With incorporation of 0.1 wt% AgNPs, a five-fold increase in the tensile strength was achieved without sacrificing the ultimate strain. The WPU/Ag nanocomposite films showed antibacterial activity against Escherichia coli and Staphylococcus aureus. © 2021 Society of Industrial Chemistry.     

Improvement of mechanical,thermal and tribological properties of (3-aminopropyl) triethoxysilane-modified graphene/polyimide nanocomposites by in situ polymerisation

To elucidate the improvement and the principle of graphene modification on the polyimide (PI), (3-aminopropyl) triethoxysilane-modified graphene (PMG), was designed and prepared by anchoring the (3-aminopropyl) triethoxysilane (APTS) chain on the graphene sheet surface, and used to synthesise PI composites by in situ polymerisation. The unique surface modification significantly improved the compatibility and dispersion of graphene in the PI matrix. Tensile strength and Young’s modulus of 1.0PMG/PI was 109.45?MPa and 1.73?GPa, which increased by 54.26 and 86.02% from neat PI, respectively. The tribological properties and mechanism were also discussed. The friction coefficient and wear rate of 1.0PMG/PI (0.287, 2.291×10^?5mm³?Nm^?1) decreased by 47.53% and 35.06%, respectively. This improvement of the tribological properties was mainly caused by the cooperative interaction of the improved mechanical and thermal properties of the composites and the high self-lubricity of modified graphene.     

Processing–structure–properties relationships of mechanically and thermally enhanced smectite/epoxy nanocomposites

Mechanically reinforced and thermally enhanced smectite/epoxy nanocomposites were synthesized using “direct” (without solvent) and “solvent” processing techniques. The molecular dispersion of smectite clay in the epoxy resin was investigated for its role in the rheology, structure formation, and properties of nanocomposites. The effects of three types of organic modifiers on the dispersion structure were compared. The use of solvent during processing assists in the enhancement of clay exfoliation. Rheology was used as a method to compare the degree of clay delamination in the resin matrix, as well as to estimate the suspension structure. The critical volume fraction (Φ*) and maximal packaging of smectites were determined and used for prediction of the viscosity. The qualitative changes in the nanostructure of suspensions above Φ*, due to flocculation of exfoliated clay layers, were compared with the alteration of the properties of nanocomposites, related to the structure formation and morphology. The curing kinetics were found to depend on both the organic modifier and solvent, but the extent of curing was roughly equivalent for the pure epoxy resin and the nanocomposites. The structure of the nanocomposites, either intercalated or exfoliated, produced by the direct processing technique was controlled by the organic modifier. By using solvent processing, the effect of the solvent dominates that of the organic modifier, presumably leading to exfoliated nanocomposites. The mechanical and thermal properties are strongly enhanced above the Φ* of smectites, and they are significantly dependent on the type of nanocomposite structure and the use of solvent. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2499–2510, 2005     

Facile synthesis of three dimensional flower-like Co3O4@MnO2 core-shell microspheres as high-performance electrode materials for supercapacitors

In this work, we reported the synthesis of three dimensional flower-like Co₃O₄@MnO₂ core-shell microspheres by a controllable two-step reaction. Flower-like Co₃O₄ microspheres cores were firstly built from the self-assembly of Co₃O₄ nanosheets, on which MnO₂ nanosheets shells were subsequently grown through the hydrothermal decomposition of KMnO₄. The MnO₂ nanosheets shells were found to increase the electrochemical active sites and allow faster redox reaction kinetics. Based on these advantages, when used as an electrode for supercapacitors, the prepared flower-like Co₃O₄@MnO₂ core-shell composite electrode demonstrated a significantly enhanced specific capacitance (671 F g⁻¹ at 1 A g⁻¹) as well as improved rate capability (84% retention at 10 A g⁻¹) compared with the pristine flower-like Co₃O₄ electrode. Moreover, the optimized asymmetric supercapacitor device based on the flower-like Co₃O₄@MnO₂//active carbon exhibited a high energy density of 34.1 W h kg⁻¹ at a power density of 750 W kg⁻¹, meaning its great potential application for energy storage devices.     

Synthesis and characterization of (Fe3O4/MWCNTs)/ epoxy nanocomposites

A sonochemical technique is used for in situ coating of iron oxide (Fe₃O₄) nanoparticles on outer surface of MWCNTs. These Fe₃O₄/MWCNTs were characterized using a high‐resolution transmission electron microscope (HRTEM), X‐ray diffraction, and thermogravimetric analysis. The as‐prepared Fe₃O₄/MWCNTs composite nanoparticles were further used as reinforcing fillers in epoxy‐based resin (Epon‐828). The nanocomposites of epoxy were prepared by infusion of (0.5 and 1.0 wt %) pristine MWCNTs and Fe₃O₄/MWCNTs composite nanoparticles. For comparison purposes, the neat epoxy resin was also prepared in the same procedure as the nanocomposites, only without nanoparticles. The thermal, mechanical, and morphological tests were carried out for neat and nanocomposites. The compression test results show that the highest improvements in compressive modulus (38%) and strength (8%) were observed for 0.5 wt % loading of Fe₃O₄/MWCNTs. HRTEM results show the uniform dispersion of Fe₃O₄/MWCNTs nanoparticles in epoxy when compared with the dispersion of MWCNTs. These Fe₃O₄/MWCNTs nanoparticles‐infused epoxy nanocomposite shows an increase in glass transition (T_g) temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electromagnetic wave shielding and microwave absorbing properties of hybrid epoxy resin/foliated graphite nanocomposites

The aim of this study is to prepare and characterize foliated graphite nanosheets (FGNs) reinforced composites based on epoxy resin for the electromagnetic wave shielding and microwave absorbing applications. The microstructure of as prepared FGNs and epoxy reinforced with different content of foliated graphite was examined by means of scanning electron microscopy and transmission electron microscopy. The effect of FGNs on thermal stability of composites was examined by thermal gravimetric. It is found that the inclusion of FGNs into the epoxy resin matrix enhances the microstructure core of epoxy resin composites. Static electric properties such as electrical conductivity, carrier mobility, number of charge carriers, and thermoelectric power of composites were studied in details. Dielectric properties of epoxy/FGN composites were characterized as a function of composition and frequency in the range of 1–18 GHz. The electromagnetic wave shielding as a function of frequency of composites was examined and compared with theoretical values. The highest shielding effectiveness was obtained for high foliated graphite loading sample FG40 at frequency of 18 GHz it equals to 62 dB. Finally, the electromagnetic wave properties such as absorption loss and reflection loss as a function of frequency were investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of aluminum methylcyclohexylphosphinate and its use as flame retardant for epoxy resin

A novel aluminum phosphinate—aluminum methylcyclohexylphosphinate (Al(MHP))—was synthesized by reacting n‐butyl methylphosphonite with cyclohexene, followed by reacting with anhydrous AlCl₃. The products were characterized with gas chromatography, Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, phosphorus nuclear magnetic resonance, X‐ray fluorescent spectroscopy, and thermogravimetric (TG) analyses. After blending with epoxy resin (EP), flame retardancy was estimated with the use of limited oxygen index (LOI) and UL‐94 test, and thermal stability was investigated using TG analysis. The morphologies and composition of the char obtained after being heated at 300 °C for 20 min followed by 500 °C for 3 min in the muffle furnace were characterized by scanning electron microscopy (SEM) with energy‐dispersive X‐ray (EDX) analysis. Results showed that Al(MHP) is an efficient flame retardant for EP, and Al(MHP)/EP can pass UL‐94V‐0 rating with an LOI of 28.8% by adding 15 wt.% of Al(MHP). TG results showed that the presence of Al(MHP) in EP increases the char yield and depresses the thermal decomposition. SEM‐EDX analysis showed that the char obtained at 300 °C is coherent and consists of P‐rich components; at higher temperature (500 °C), the char becomes tiny and loose and phosphorus element is released into gas. Compared with neat EP, composites have lower water absorption. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermal and mechanical properties of polyamide 12/graphene nanoplatelets nanocomposites and parts fabricated by fused deposition modeling

The printable polyamide 12 (PA12) nanocomposite filaments with 6 wt % graphene nanoplatelets (GNPs) for fused deposition modeling (FDM) were prepared by melting compounding and smoothly printed via a commercial FDM three‐dimensional (3D) printer. The thermal conductivity (λ) and elastic modulus (E) of 3D printed PA12/GNPs parts along to the printing direction had an increase by 51.4% and 7% than that of compression molded parts, which is due to the GNPs preferentially aligning along to the printing direction. Along with these improved properties, ultimate tensile strength of 3D printed PA12/GNPs parts was well maintained. These results indicate that FDM is a new way to achieve PA12/GNPs parts with enhanced λ over compression moulding, which could contribute to realize efficient and flexible heat management for a wide range of applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45332.     

Thermal and mechanical properties of poly(urethane‐imide)/epoxy/silica hybrids

Improving properties of polyurethane (PU) elastomers have drawn much attention. To extend the properties of the modified PU composite, here a new method via the reaction of poly(urethane‐imide) diacid (PUI) and silane‐modified epoxy resin (diglycidyl ether of bisphenol A) was developed to prepare crosslinked poly (urethane‐ imide)/epoxy/silica (PUI/epoxy/SiO₂) hybrids with enhanced thermal stability. PUI was synthesized from the reaction of trimellitic anhydride with isocyanate‐terminated PU prepolymer, which was prepared from reaction of polytetramethylene ether glycol and 4,4′‐diphenylmethane diisocyanate. Thermal and mechanical properties of the PUI/epoxy/SiO₂ hybrids were investigated to study the effect of incorporating in situ SiO₂ from silane‐modified epoxy resin. All experimental data indicated that the properties of PUI/epoxy/SiO₂ hybrids, such as thermal stability, mechanical properties, were improved due to the existence of epoxy resin and SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010