Structure and mechanical properties of brittle starch foams

The mechanical properties of extrusion-cooked maize have been analysed according to the Gibson and Ashby models of closed cell foams. The data point to better agreement with the earlier model and indicate that the cell-face bending term is not negligible for foams with little draining into the cell edges. The shape of the cells in these maize foams changes with foaming conditions: non-equilibrium spherical cells with some anisotropy are formed at conditions of low moisture content or high temperature when the glass transition temperature, T _g, is elevated. Polyhedral cells which show some draining of material into the cell edges are formed under the converse conditions when the T _g is lower. The change from polyhedral to spherical cells is also accompanied by a change in amylose-lipid complex from the V to the metastable E type, as shown by X-ray diffraction.     

Thermoanalytical characterization of epoxy matrix-glass microballoon syntactic foams

Syntactic foams are finding new applications where their thermal stability and high temperature response are important. Therefore, the high temperature response of these advanced composites needs to be characterized and correlated with various material parameters. The present study is aimed at evaluating the effect of microballoon (hollow particle) volume fraction (Φ) and wall thickness (w) on thermoanalytical characteristics of epoxy matrix syntactic foams containing glass microballoons. These composites are characterized to determine the glass transition temperature (T _g), the weight loss, and the char yield. It is observed that T _g decreases and the char yield increases due to the presence of microballoons in the resin. The T _g is increased with an increase in Φ but is not significantly affected by w. The thermal stability is increased by increasing w and is relatively less sensitive to Φ. Understanding the relations between thermal properties of syntactic foams, the microballoon wall thickness, and microballoon volume fraction will help in developing syntactic foams optimized for mechanical as well as thermal characteristics. Due to the increased interest in functionally graded syntactic foams containing a gradient in microballoon volume fraction or wall thickness, the results of the present study are helpful in better tailoring these materials for given applications.     

Characterization of epoxy syntactic foams by dynamic mechanical analysis

Epoxy syntactic foams that are capable of withstanding use-temperatures in the range of 106 to 175°C were fabricated with DGEBA or novolac based epoxy resins and appropriate amine hardener materials. These foams were characterized for dynamic mechanical properties in single cantilever mode. The storage modulus, loss modulus and tan δ values were recorded over a wide temperature range. A typical density value of around 0.45 g/cm³ of the syntactic foams made respectively from a cycloaliphatic amine hardener, aromatic amine hardener-I, aromatic amine hardener-II recorded storage modulus (E′) values of 1354 MPa, 1500 MPa and 1530 MPa respectively and tan δ values of 0.0139, 0.0090, 0.01039 respectively at 30°C. The storage modulus values gradually decreased with increasing temperature while the loss modulus values showed corresponding gradual increase in the same temperature range. There is a steep variation in these values when the material softens in the vicinity of the glass transition temperature (T _g) indicating the upper temperature limits to which they can be put in use. The reduction in the storage modulus values with increasing temperature and the glass transition temperature values are characteristic of the resin/hardener systems as well as the curing/post curing cycles employed.     

Thermal stress hysteresis and stress relaxation in an epoxy film

Thermal cycling of an epoxy coating on silicon through the glass transition temperature (T _g) revealed a large stress hysteresis on the first thermal cycle through T _g and a change in the stress–temperature slope at T _g resulting from the change in the epoxy elastic properties due to the glass transition. This stress hysteresis was not observed on subsequent thermal cycles through T _g. However, after the coating was annealed (aged) below T _g (for hours or longer)—during which the stress relaxed exponentially with time—the stress hysteresis returned. The magnitude of stress hysteresis, on cycling through T _g, was found to correlate to the magnitude of long-time relaxation that occurred during annealing at temperatures below T _g.     

Processing-structure relationships for multiphase epoxy matrix systems

A styrene-modified diglycidyl ether of bisphenol-A (DGEBA) epoxy system cured with trimellitic anhydride (TMA) has been investigated to explore processing and structure relationships. During cure, the reactive styrene precipitated with polymerization into phase domains separate from the epoxy phase. Dynamic mechanical analysis and microscopy studies were performed to gain insight to matrix structure. The DMA studies showed that the styrenemodified epoxy system after cure exhibited two partially overlapped but distinct relaxation peaks, which are associated with the T _gs of the polystyrene and epoxy phases. The glass transition of the polystyrene phase was shown to be broadened and the T _g to depend strongly on processing temperature profiles. While the T _g of the epoxy phase increases with curing agent concentrations, the T _g of the polystyrene phase does not. Microscopic studies showed that the styrene-modified system exhibited a rougher fracture surface but did not reveal well defined phase domains in which the precipitated polystyrene component was aggregated. Overall, the study has demonstrated correlations of the kinetic factors in controlling the morphology in reactive modifier-epoxy systems.     

The β-relaxation in epoxy resins; the temperature and time-dependence of cure

Internal friction and creep measurements have been used to reveal the mechanism of cure in epoxy resins cross-linked with diethylene triamine (DETA). The -relaxation is associated with the main glass transition of the undercured resin network. The glass transition temperature (T _g) is about 40° C above the maximum temperature of cure and the curing reaction slows down about 2 h after each increase of the temperature. At 25° C the cure is only about half complete and since in this resin, when fully cross-linked, T _g is at about 140° C, temperatures of 100° C or over are needed to complete cure.     

Influences of cellulose nanofiber on the epoxy network formation

The effects of cellulose nanofiber on the curing behavior, dynamic mechanical, and morphology properties of epoxy/diamine systems were investigated. The studies were conducted using an aliphatic triamine, diethylentriamine (Dien), and an aromatic diamine, diaminodiphenylmethan (DDM), as the curing agents in the presence of three different levels of 0.5, 2, and 5 phr of cellulose nanofiber. Calorimetry experiments were used to probe the changes in the reaction enthalpy and in the glass transition temperature (T_g) as a function of the fiber concentration. The results showed that both the T_g and the heat of reaction were increased with increasing the fiber concentration up to 2 phr. The experimental cure data obtained from in situ FT-IR measurements were used to evaluate the kinetic parameters using the modified Avrami theory of phase change. The results showed that the kinetic parameters were less sensitive to the epoxy composition. DMTA measurements showed that the storage modulus and the T_g of the composites were dependant on the level of fiber loading. SEM studies revealed that a reasonable dispersion and adhesion have been achieved between the fiber and the epoxy matrix at low concentration of fiber. It is concluded that the fiber agglomerated at high concentration of cellulose fiber prevented the formation of a homogeneous mixture, thus resulting in weak thermal and mechanical properties.     

High-pressure autoclave curing for a thermoset composite: effect on the glass transition temperature

The effect of high-pressure curing within an autoclave on the cured glass transition temperature (T _g) of a thermoset fibre-reinforced composite has been studied. The results indicate that an increase in the T _g value was obtained by a higher curing pressure as well as a lower moisture content. Both results have been related to the reduction in the microscopic free volume and the macroscopic void content of the matrix resin. Using the results obtained, the T _g increase was related to the applied autoclave pressure through equations based on both free-volume and thermodynamic concepts, with the results indicating a significantly higher effect than for homogeneous polymers. This has been attributed to a moisture-dominant diffusion process which has been used to explain the growth and reduction of voids.     

Dielectric response of Ag/BaTiO<Subscript>3</Subscript>/epoxy nanocomposites

Dielectric properties and relaxation phenomena of hybrid material (functionalized nanosilver/BaTiO₃/epoxy) were studied as a function of ceramic content. Nanoparticles were obtained through chemical reduction in ethanol and triethylenetetramine. Epoxy resin, functionalized Ag and BaTiO₃ were mixed and composites were prepared onto glass substrates by dipping technique. Samples containing various amounts of ceramic filler were examined by thermal and SEM analysis. Dielectric measurements were performed at different frequencies and temperatures. It was found that hybrid materials had high permittivities and their relaxation processes were influenced by the epoxy resin near its T _g, while metallic and ceramic content modified the real permittivity values.     

Curing characteristics of an epoxy resin in the presence of ball-milled graphite particles

The effects of simply-made graphite particles (GPs, 1 wt%) on curing kinetics of an epoxy resin were investigated by means of differential scanning calorimetry (DSC). Two approaches based on constant and variable activation energy were applied to analyze the DSC curves. Results from the constant energy method showed that addition of the GPs increased the activation energy E _c and the overall order of reaction m + n. With the variable energy method, the activation energy varied with curing conversion substantially in the GP/epoxy system; in contrast, the variation in the pure epoxy was very limited. The GPs also decreased the heat of reaction (ΔH) and increased the glass transition temperature (T _g) for the epoxy. Comprehensive analyses indicated that the GPs did not significantly impede the curing reaction, which can enable improvement of the composite functionalities without creating processing penalties. The information obtained from this study provides an understanding of multiple factors involved in the complex relationship of structure and properties of the composites.     

Service life assessment and moisture influence on bio-based thermosetting resins

In this study, three different types of bio-based resins are compared to a conventional oil-based epoxy in terms of moisture uptake, long-term properties and its influence of moisture and glass transition temperature, T _g. Moisture uptake is determined by means of gravimetric method, time temperature superposition (TTSP), and T _g data obtained in dynamic mechanical thermal analysis (DMTA). Moisture uptake show Fickian diffuison behavour for all resins, saturation level and diffusion coefficient however differ. The long-term properties is characterised by creep compliance master curves created by means of TTSP. The examined bio-based resins are compatible to the reference epoxy in term of stability up to 3–10 years. Comparison between master curves for virgin, wet, and dried material show that moisture present in the specimen increases creep rate, and that some of this increase remains after drying of samples. T _g measurements show that moisture inside the specimen decreases T _g; this is anticipated because of the plasticizing effect of water. The overall conclusions are that the bio-based resins of polyester, and epoxy type are comparable in performance with oil-based epoxy, LY556 and they can be used to develop high-performance composites.     

Temperature dependence of fracture toughness of epoxy resins cured with diamines

The fracture toughness (critical stress intensity factor, K _Ic) of epoxy resins cured with four diamines has been measured as a function of temperature over the range from –35° C to above T _g. It was found that K _Ic for each epoxy-diamine system did not vary below room temperature, and in the higher temperature range K _Ic increased with increasing temperature to a maximum and then decreased. The temperature which maximized K _Ic, agreed with the temperature at which the flexural modulus of the epoxy resins abruptly dropped. This temperature was therefore considered as T _g. This temperature was found to be about 20° C lower than the heat deflection temperature under load (1.82 M Pa) of the resins.     

Epoxy resin cured with poly(4-vinyl pyridine)

Poly(4-vinylpyridine) (P4VP) was used as the macromolecular curing agent to prepare epoxy networks. The crosslinking structures were investigated by means of Fourier transform infrared spectroscopy (FTIR). It is identified that depending on the ratios of DGEBA to P4VP, different reactions dominated the formation of the crosslinking networks, which were involved the formation of pyridone (or cyclic amide) resulting from epoxide groups of DGEBA and pyridine rings of P4VP, the Diels-Alder reaction of in situ formed conjugated 3,5-diene in a 6-member ring and the homopolymerization of DGEBA initiated by pyridine moiety of P4VP. Differential scanning calorimetry (DSC) showed that all the DGEBA-P4VP co-crosslinked thermosets displayed single glass transition temperature (T_g), suggesting that the crosslinked networks are homogenous. In addition, it is noted that the T_g's of the DGEBA-rich network are greatly dependent on the molecular weight of P4VP used.     

Synthesis of Uniquely Structured Yolk–Shell Metal Oxide Microspheres Filled with Nitrogen‐Doped Graphitic Carbon with Excellent Li–Ion Storage Performance

Novel structured composite microspheres of metal oxide and nitrogen‐doped graphitic carbon (NGC) have been developed as efficient anode materials for lithium‐ion batteries. A new strategy is first applied to a one‐pot preparation of composite (FeO_x‐NGC/Y) microspheres via spray pyrolysis. The FeO_x‐NGC/Y composite microspheres have a yolk–shell structure based on the iron oxide material. The void space of the yolk–shell microsphere is filled with NGC. Dicyandiamide additive plays a key role in the formation of the FeO_x‐NGC/Y composite microspheres by inducing Ostwald ripening to form a yolk–shell structure based on the iron oxide material. The FeO_x‐NGC/Y composite microspheres with the mixed crystal structure of rock salt FeO and spinel Fe₃O₄ phases show highly superior lithium‐ion storage performances compared to the dense‐structured FeO_x microspheres with and without carbon material. The discharge capacities of the FeO_x‐NGC/Y microspheres for the 1st and 1000th cycle at 1 A g^?1 are 1423 and 1071 mAh g^?1, respectively. The microspheres have a reversible discharge capacity of 598 mAh g^?1 at an extremely high current density of 10 A g^?1. Furthermore, the strategy described in this study is generally applied to multicomponent metal oxide–carbon composite microspheres with yolk–shell structures based on metal oxide materials.     

Glass transition evaluation of commercially available epoxy resins used for civil engineering applications

The paper presents a study about the glass transition of commercially available epoxy resins used for structural strengthening of concrete members for instance by means of Carbon Fiber Reinforced Polymer (CFRP) strips. Prior to an experimental investigation with a dynamic mechanical analysis (DMA), an overview on differences between definitions for the glass transition temperature T_g is given. Several testing recommendations are listed in this respect. Subsequently, DMA tests on three commercially available products are presented. A first focus is put on the different evaluation methods for one specific test result. It is visible that considerable differences in the finally adapted glass transition temperature might arise if one or the other procedure is followed. Additional parameters, such as curing procedure, specimen age, temperature history, and ultimate temperature during heating are considered, too. In all the above mentioned cases, differences in the glass transition can be found. Higher specimen age, higher ultimate temperature during testing, accelerated curing, as well as a lower heating rate implicate higher glass transition temperatures, showing that the glass transition temperature is not a fixed material characteristic. In a final step, the relevance for T_g for civil engineering applications is described. The various design code provisions for defining the service temperature in structures related to T_g are presented. The overall aim of the investigation is to show that structural engineers and end users have to be aware of the different influential parameters on the final results regarding the glass transition temperature, which also highlights the need of a potential deeper product investigation in case technical data sheets lack detailed information.     

Extremely Small Pyrrhotite Fe7S8 Nanocrystals with Simultaneous Carbon‐Encapsulation for High‐Performance Na–Ion Batteries

Na/FeS_x batteries have remarkable potential applicability due to their high theoretical capacity and cost‐effectiveness. However, realization of high power‐capability and long‐term cyclability remains a major challenge. Herein, ultrafine Fe₇S₈@C nanocrystals (NCs) as a promising anode material for a Na–ion battery that addresses the above two issues simultaneously is reported. An Fe₇S₈ core with quantum size (≈10 nm) overcomes the kinetic and thermodynamic constraints of the Na‐S conversion reaction. In addition, the high degree of interconnection through carbon shells improves the electronic transport along the structure. As a result, the Fe₇S₈@C NCs electrode achieves excellent power capability of 550 mA h g^?1 (≈79% retention of its theoretical capacity) at a current rate of 2700 mA g^?1. Furthermore, a conformal carbon shell acts as a buffer layer to prevent severe volume change, which provides outstanding cyclability of ≈447 mA h g^?1 after 1000 cycles (≈71% retention of the initial charge capacity).     

Multiscale molecular modeling of SWCNTs/epoxy resin composites mechanical behaviour

Atomistic and mesoscale simulations were conducted to estimate the effect of the diameter and weight fraction of single walled carbon nanotubes (SWCNTs) on mechanical behaviour and glass transition temperature (T_g) of SWCNTs reinforced epoxy resin composites. Atomistic periodic systems of epoxy resin and epoxy resin/SWCNTs were built with different weight ratios and were subject of an extensive multistage equilibration procedure. Molecular dynamics simulations were used to estimate glass transition temperature, Young modulus and solubility parameter of epoxy resin and epoxy resin/SWCNTs composites. Dissipative particle dynamics method and Flory–Huggins theory was employed to predict epoxy resin/SWCNTs morphologies. The results show that incorporation of SWCNTs with diameters ranging from 10 to 14 ? has beneficial effect on mechanical integrity and T_g. Overall, the agreement between predicted material properties and experimental data in the literature is very satisfactory.     

Multiscale molecular modeling of SWCNTs/epoxy resin composites mechanical behaviour

Atomistic and mesoscale simulations were conducted to estimate the effect of the diameter and weight fraction of single walled carbon nanotubes (SWCNTs) on mechanical behaviour and glass transition temperature (T_g) of SWCNTs reinforced epoxy resin composites. Atomistic periodic systems of epoxy resin and epoxy resin/SWCNTs were built with different weight ratios and were subject of an extensive multistage equilibration procedure. Molecular dynamics simulations were used to estimate glass transition temperature, Young modulus and solubility parameter of epoxy resin and epoxy resin/SWCNTs composites. Dissipative particle dynamics method and Flory–Huggins theory was employed to predict epoxy resin/SWCNTs morphologies. The results show that incorporation of SWCNTs with diameters ranging from 10 to 14 Ǻ has beneficial effect on mechanical integrity and T_g. Overall, the agreement between predicted material properties and experimental data in the literature is very satisfactory.     

Co Nanoparticles Confined in 3D Nitrogen‐Doped Porous Carbon Foams as Bifunctional Electrocatalysts for Long‐Life Rechargeable Zn–Air Batteries

Proper design and simple preparation of nonnoble bifunctional electrocatalysts with high cost performance and strong durability for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is highly demanded but still full of enormous challenges. In this work, a spontaneous gas‐foaming strategy is presented to synthesize cobalt nanoparticles confined in 3D nitrogen‐doped porous carbon foams (CoNCF) by simply carbonizing the mixture of citric acid, NH₄Cl, and Co(NO₃)₂·6H₂O. Thanks to its particular 3D porous foam architecture, ultrahigh specific surface area (1641 m² g^?1), and homogeneous distribution of active sites (C–N, Co–N_x, and Co–O moieties), the optimized CoNCF‐1000‐80 (carbonized at 1000 °C, containing 80 mg Co(NO₃)₂·6H₂O in precursors) catalyst exhibits a remarkable bifunctional activity and long‐term durability toward both ORR and OER. Its bifunctional activity parameter (ΔE) is as low as 0.84 V, which is much smaller than that of noble metal catalyst and comparable to state‐of‐the‐art bifunctional catalysts. When worked as an air electrode catalyst in rechargeable Zn–air batteries, a high energy density (797 Wh kg^?1), a low charge/discharge voltage gap (0.75 V), and a long‐term cycle stability (over 166 h) are achieved at 10 mA cm^?2.