酸化处理对纳米碳纤维及其复合材料性能的影响

本文采用浓酸(浓硫酸/浓硝酸)氧化法对纳米碳纤维进行表面处理,在水热和超声分散条件下,制备纳米碳纤维/环氧树脂复合材料.X射线光电子能谱分析表明,酸化处理在纳米碳纤维表面引入了羟基和羧基等能参与环氧树脂固化反应的官能团.流变试验结果表明,酸化处理在一定程度上提高了复合材料流体的流动性.断裂韧性测试结果和扫描电子显微镜(SEM)分析也显示了酸化处理能有效改善纤维与树脂的界面结合状况,提高复合材料的断裂韧性.     

Polyaniline‐modified cellulose nanofibrils as reinforcement of a smart polyurethane

Segmented polyurethanes exhibiting shape memory properties were modified by the addition of polyaniline (PANI)‐coated cellulose nanofibrils (CNFs). The two‐phase structure of the polymer is responsible for the material's ability to ‘remember’ and autonomously recover its original shape after being deformed in response to an external thermal stimulus. PANI was grown on the surface of the CNFs via in situ polymerization. Modified nanocrystals were added to the segmented polyurethane in concentrations ranging from 0 to 15 wt%. The changes in the material properties associated with the percolation of the coated fibrils appear at higher concentrations than previously observed for non‐modified CNFs, which suggests that fibril agglomeration is occurring due to the PANI coating. The shape memory behavior of the composites is maintained at about the same level as that of the unfilled polyurethane only up to 4 wt% of fibrils. At higher concentrations, the rigidity of the nanofibrils as well as their interaction with the hard‐segment phase and the increasing difficulty of dispersing them in the polymer collaborate to produce early breakage of the specimens when stretched at temperatures above the melting point of the soft segments. Copyright © 2010 Society of Chemical Industry     

Cure kinetics of epoxy resin used for advanced composites

The cure kinetics of an epoxy resin used for the preparation of advanced polymeric composite structures was studied by isothermal differential scanning calorimetry (DSC). A series of isothermal DSC runs provided information about the kinetics of cure over a wide temperature range. According to the heat evolution behavior during the curing process, several influencing factors of isothermal curing reactions were evaluated. The results showed that the isothermal kinetic reaction of this epoxy resin followed an autocatalytic kinetic mechanism. In the latter reaction stage, the curing reaction became controlled mainly by diffusion. Cure rate was then modeled using a modified Kamal autocatalytic model that accounts for the shift from a chemically controlled reaction to a diffusion‐controlled reaction. The model parameters were determined by a nonlinear multiple regression method. Copyright © 2004 Society of Chemical Industry     

等温DSC法研究液态橡胶改性环氧树脂固化动力学

用等温差示扫描量热法(DSC)在三个不同的固化温度下研究了不同含量端羧基液态橡胶(CTBN)改性环氧树脂的等温固化过程,考察了不同CTBN含量对环氧树脂固化动力学的影响。通过Kamal方程对不同含量CTBN改性环氧树脂固化过程数据进行拟合,得到反应速率常数k1、k2及反应级数m、n,计算得到反应活化能的值,结果表明CTBN质量分数由0%到20%,k1、k2逐渐增大,反应前期活化能由67.34kJ/mol增加到80.31kJ/mol,增加了19.26%,反应后期活化能由94.19kJ/mol增加到180.07kJ/mol,增加了91.18%。     

Carbon nanofiber paper and its effect on cure kinetics of low temperature epoxy resin

In this study, the preparation, properties, and characterization of thin films or “nanopapers” of carbon nanofibers (CNFs) were studied. Specifically, a layer-by-layer nanopaper preparation method was used, which significantly improved the mechanical properties of nanopapers. The effect of CNF nanopaper on the cure kinetics of a low temperature epoxy resin was studied. A modified autocatalytic model was used to represent the reaction kinetics. It was found that the presence of CNF nanopaper substantially increased the resin reaction rate and final conversion. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on the cure kinetics and networks properties of neat and polydimethylsioxane modified tetrafunctional epoxy resins

The cure kinetics of tetrafunctional epoxy resins with three different backbone structures and their modification by polydimethylsioxane (PDMS) were studied by means of differential scanning calorimetry with dynamic approach. The development of epoxy networks was characterized by dynamic viscoelastic measurements. Results showed that all the epoxy resins obeyed the autocatalytic reaction mechanism with a reaction order of about 3. Epoxy resin with softer aliphatic backbone demonstrated a higher cure reactivity and stronger tendency towards autocatalysis, as well as lower crosslinking density. The PDMS‐modified epoxy resins showed higher early cure reactivity and a lower crosslinking density due to the plasticization and restriction effect of the dispersed PDMS phase, respectively. Based on cure kinetics and dynamic viscoelastic results, the α_m was found to be an effective precursor for describing the developing of epoxy networks during the course of cure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Epoxy curing by polyaniline (PANI) – Characterization and self-healing evaluation

Polyaniline (PANI) was synthesized by chemical oxidative polymerization of aniline dissolved in aqueous phosphoric acid. The polymer was characterized by UV–Visible spectroscopy (UV–Vis), thermal gravimetric analysis (TGA) and Fourier transform infrared spectroscopic (FTIR) techniques. Hardener free epoxy coating was formulated with 10% PANI. The curing process of epoxy resin by PANI was analyzed using FTIR and a suitable mechanism of curing was suggested. The corrosion protective performance of conventional polyamide cured epoxy and PANI cured epoxy coating on steel has been assessed in 3% NaCl by electrochemical impedance spectroscopy (EIS). The self-healing property of the PANI cured epoxy coating on steel in 3% NaCl was studied by scanning vibrating electrode technique (SVET).     

Investigation of corrosion protection performance of epoxy coatings modified by polyaniline/clay nanocomposites on steel surfaces

In this study, polyaniline (PANI) and polyaniline/clay nanocomposites were prepared via in situ oxidative polymerization. The morphology of nanocomposites structures was investigated by X-ray diffraction (XRD). The chemical structures of PANI and PANI/clay nanocomposites were examined via Fourier transform infrared (FT-IR) spectroscopy. Polyaniline-based pigments were introduced into epoxy paint and applied on steel substrates. The effect of clay addition and the type of clay cation, including Na⁺ in natural clay (MMT) and alkyl ammonium ions in organo-modified montmorillonite (OMMT), on the anticorrosion performance of epoxy-based coatings was investigated through electrochemical Tafel test, electrochemical impedance spectroscopy and immersion measurements in NaCl solution. The stability of the adhesion of the neat and modified epoxy coatings to the steel surface was also examined. The results indicated that introduction of PANI/OMMT nanocomposite into epoxy paint results in improved anticorrosion properties in comparison with PANI/MMT and neat PANI.     

Thermal analysis of curing process of epoxy prepreg

The curing process of epoxy prepreg was studied by means of differential scanning calorimetry analysis. The dynamic, isothermal, and combinations of dynamic and isothermal measurements were done over selected temperature ranges and isothermal cure temperatures. The heats of reaction for dynamic and isothermal cure were determined. The results show that the heat of the isothermal‐cure reaction increased with the increment of temperature. The degree of cure was calculated from the heat of the isothermal‐cure reaction. The complete cure reaction could be achieved at 220°C within a very short cure time. The changes of cure rate with time were given for the studied isothermal cure temperatures. To simulate the relationship between the cure rate and degree of cure, the autocatalytic model was used and the four parameters were calculated. Except in the late stage of the cure reaction, the model agrees well with the experimental data, especially at high temperatures. To account for the effect of diffusion on the cure rate, a diffusion factor was introduced into the model. The modified model greatly improved the predicted data at the late stage of cure reaction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1074–1083, 2002     

Synthesis and characterization of polyaniline nanorods as curing agent and nanofiller for epoxy matrix composite

Novel PANI nanorods with average diameter of 21-53 nm and length of 0.5-1 μm were synthesized by dispersion polymerization method. The morphology of obtained PANI nanorods was significantly dependent on the type of salt, stirring, and polymerization temperature. Dispersion polymerization with FeCl₃ produced longer nanorods than ammonium persulfate (APS) and magnetic stirring decreased the length of nanorods. While the average diameter of PANI nanorods decreased with increasing reaction temperature, the electrical conductivity dropped considerable at high polymerization temperature due to the increment of insulating emeraldine base. Dynamic differential scanning calorimetry (DSC) study showed that the heat of cure was independent of heating rate. On the contrary, the heat of cure was proportional to the content of PANI nanorods as a role of curing agent. Isothermal DSC study revealed that the cure behavior of LCE/PANI nanorod system was an auto-catalyzed reaction. Thermogravimetric analysis (TGA) indicated that the thermal stability of cured LCE/PANI nanocomposite was significantly dependent on the PANI nanorod composition. In addition, the electrical conductivity of LCE/PANI nanocomposite materials was higher than that of conventional epoxy composites. Therefore, PANI nanorods played a role of curing agent owing to the existent amine group and acted as reinforcing filler for cured LCE nanocomposites.     

Application of the kinetic composite methodology to autocatalytic-type thermoset prepreg cures

Using a commercial epoxy/carbon fiber prepreg as a model system, cure kinetics of an autocatalytic-type reaction were analyzed by a general form of conversion-dependent function first proposed for degradation kinetics of polymers and composites. The characteristic feature of conversion-dependent function was determined using a reduced-plot method where the temperature-dependent reaction rate constant was analytically separated from the isothermal data. Assuming two elementary reaction mechanisms that were expressed by the nth order and autocatalytic kinetic models, they were combined with a composite methodology capable of predicting overall kinetic behavior. The activation energies were determined and favorably compared for both isothermal and dynamic-heating differential scanning calorimetry experiments in the temperature region for standard epoxy cures at 177°C (350°F). Finally, the proposed model equation demonstrated excellent predictive capability and broad applicability in describing various types of thermoset polymer cure for both isothermal and dynamic heating conditions. © 1993 John Wiley & Sons, Inc.     

In-process control of epoxy composite by microdielectrometric analysis

The curing of an epoxy prepolymer based on the diglycidyl ether of bisphenol A (DGEBA) with dicyandiamide (DDA) as the hardener and imidazole as the catalyst agent was analyzed using microdielectrometry, differential scanning calorimetry, viscosity measurements, and insolubles in THF for gel-point detection. Interpreting dielectric data with respect to chemorheology continues to be the subject of scientific discussion. The focus of this issue is to give an industrial point of view on the collected on-line dielectric measurements during an epoxy/fiber glass composite cure. Hence, isothermal polymerizations of DGEBA/DDA/imidazole resin were examined and dielectric properties such as ionic conductivity were related to the cure kinetics by conversion through an experimentally established equation. This mathematical model was used to predict reaction advancement of epoxy processing under nonisothermal cure conditions. This model is shown to be able to forecast both isothermal and nonisothermal cure data of unaged resin. According to these results, cure monitoring was carried out on prepregs. Whereas some deviations of the law were observed at the time of the last stage of the cure, good correlation was obtained for the reaction rate during the in-mold process curing time.     

Interphase cure characterization in epoxy composites by fluorescence technique

Monitoring the reaction of an aromatic diamine cure agent with epoxy by fluorescence technique was used for cure characterization of the interphase in epoxy/glass and epoxy/carbon composites. The effect of the various surface treatments was first studied by the model interphase obtained by using a quartz plate for glass or a modified quartz plate for carbon surface. Aminosilane treated quartz cured faster and showed increased cure extent, while water aging and air oxidation showed almost no effect on the cure kinetics in comparison to the untreated quartz surface. For a model carbon surface, air oxidation showed a faster reaction only at the early stage of cure. The effects of the various surface treatments on glass or carbon fiber were also studied with the actual composites made by a thin coating of epoxy-diamine melt on glass or carbon fiber bundles. Epoxy/glass fiber composite showed a similar trend as the model interphase system. In the case of epoxy/carbon fiber composite, both air oxidation and water aging treatment showed a faster cure reaction at the early stage of cure. Furthermore, air oxidation treatment for the epoxy/carbon fiber composite showed somewhat increased cure extent. The reasons for these trends have been discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1769–1775, 1997     

Enhanced oxygen reduction performance of Pt catalysts by nano-loops formed on the surface of carbon nanofiber support

We demonstrate a modification of the exposed graphite edges on herringbone carbon nanofiber (CNFs) into graphitic loops with nanosized curvature through thermal treatment. It was found that Pt catalysts supported on the surface modified CNFs showed much enhanced performance on oxygen reduction reaction. Such enhancement was possibly originated from an enhanced surface diffusion of oxygen on the modified CNFs.     

Effect of carbon nanofiber (CNF) silanization on the properties of CNF/epoxy nanocomposites

Carbon nanofibers (CNFs) were functionalized by a multistage process including oxidation, reduction and silanization. The chemical modifications were examined by Fourier transform infrared spectroscopy, X‐ray photoelectron spectrometry, Raman spectroscopy and thermogravimetric analysis. The silanized CNFs were then added into an epoxy resin (EPON 828) to study the effect of the surface modification of CNFs on the properties of nanocomposites. For comparison, nanocomposites containing original unmodified CNFs were also investigated. Scanning electron microscopy indicates better dispersion of modified fibers in the epoxy polymer matrix; the mechanical and thermal properties of composites are also improved; the electrical conductivity of the composites is reduced. Copyright © 2011 Society of Chemical Industry     

Cure kinetics and conductivity of rigid rod epoxy with polyaniline as a curing agent

The samples of rigid rod epoxy resin (4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP)) with different weight contents of polyaniline (PANI) as a curing agent were prepared. The kinetics of curing reaction between TMBP and PANI was analyzed by dynamic differential scanning calorimetry in the temperature range of 25–300°C. The results showed that the heat of cure reaction of TMBP/PANI sample with 10 wt% PANI was larger than those of others. The active energies with different curing conversions of TMBP/PANI sample with 10 wt% PANI were calculated by iso‐conversional method using the Coats‐Redfern approximation. The results showed that the activation energy was dependent on the degree of conversion. The morphology of the cured samples was detected by scanning electron microscopy measurements. The relationship between morphology and conductivity of cured samples was researched. The conductivities increased from 2.7 × 10⁻⁴ to 9.5 × 10⁻⁴ S/cm with the increase of PANI from 5 to 20 wt% in cured samples. The thermal stabilities of cured TMBP/PANI samples were examined by thermogravimetric analysis. The results showed that the cured TMBP/PANI can be promising to use as a conducting adhesive. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Curing kinetics and viscosity change of a two‐part epoxy resin during mold filling in resin‐transfer molding process

The curing kinetics and the resulting viscosity change of a two‐part epoxy/amine resin during the mold‐filling process of resin‐transfer molding (RTM) of composites was investigated. The curing kinetics of the epoxy/amine resin was analyzed in both the dynamic and the isothermal modes with differential scanning calorimetry (DSC). The dynamic viscosity of the resin at the same temperature as in the mold‐filling process was measured. The curing kinetics of the resin was described by a modified Kamal kinetic model, accounting for the autocatalytic and the diffusion‐control effect. An empirical model correlated the resin viscosity with temperature and the degree of cure was obtained. Predictions of the rate of reaction and the resulting viscosity change by the modified Kamal model and by the empirical model agreed well with the experimental data, respectively, over the temperature range 50–80°C and up to the degree of cure α = 0.4, which are suitable for the mold‐filling stage in the RTM process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2139–2148, 2000     

Cure kinetics,gelation, and glass transition of a bisphenol F epoxide

Phenomenological cure kinetic relations for a commercially available amine‐cured epoxy were developed independently using differential scanning calorimetry (DSC) in isothermal and dynamic (constant heating rate) modes and using numerical optimization techniques. The resulting model was found to be independent of the method used to collect reaction rate data. The model was modified at high temperature to account for an observed deviation from Arrhenius behavior. The cure dependence of the glass transition of the material was also investigated with DSC. The gel point as measured by parallel plate rheometry was found to occur at a degree of cure of 0.71, a value significantly advanced from a simple Flory prediction based on the functionality of the cross‐linking agent.     

Analysis of the cure of epoxy based layered silicate nanocomposites: Reaction kinetics and nanostructure development

The cure reaction kinetics of epoxy resin, with organically modified montmorillonite loadings of up to 20 wt % and with stoichiometric conditions, has been studied by differential scanning calorimetry with a view to understanding further the fabrication of epoxy‐based polymer layered silicate nanocomposites. The kinetic analysis of isothermal and nonisothermal cure shows that the autocatalytic model is the more appropriate to describe the kinetics of these reactions, and it is observed that a dominant effect of the montmorillonite is to catalyze the curing reaction. However, it was not possible to model the reactions over the whole range of degrees of conversion, in particular for nonisothermal cure. This attributed to the complexity of the reactions, and especially to the occurrence of etherification by cationic homopolymerization catalyzed by the onium ion of the organically modified montmorillonite. The homopolymerization reaction results in an excess of diamine in the system, and hence in practice the reaction is off stoichiometric, which leads to a reduction in both the heat of cure and the glass transition temperature as the montmorillonite content increases. Small angle X‐ray scattering of the cured nanocomposites shows that an exfoliated nanostructure is obtained in nonisothermal cure at slow heating rates, whereas for nonisothermal cure at faster heating rates, as well as for isothermal cure at 70°C and 100°C, a certain amount of exfoliation is accompanied by the growth of d‐spacings of 1.4 nm and 1.8 nm for dynamic and isothermal cure, respectively, smaller than the d‐spacings of the modified clay before intercalation of the resin. A similar nanostructure, consisting of extensive exfoliation accompanied by a strong scattering at distances less than the d‐spacing of the modified clay, is also found for resin/clay mixtures, before the addition of any crosslinking agent, which have been preconditioned by storage for long times at room temperature. The development of these nanostructures is attributed to the presence of clay agglomerations in the original resin/clay mixtures and highlights the importance of the quality of the dispersion of the clay in the resin in respect of achieving a homogeneous exfoliated nanostructure in the cured nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of cure reactions of anhydride/epoxy/polyetherimide blends

The cure kinetics of blends of epoxy (diglycidyl ether of bisphenol A)/anhydride (nadic methyl anhydride) resin with polyetherimide (PEI) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of PEI in the blends, the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/PEI blends indicate that PEI hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending PEI with epoxy resin, and the value was approximately 1.0. The value of n for the nth order component in the autocatalytic analysis was increased by increasing the amount of PEI in the blends, and the value increased from 1.6 to 4.0. A diffusion‐controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/PEI blends. Complete miscibility was observed in the uncured blends of epoxy/PEI at elevated temperatures up to 120 °C, but phase separations occurred in the early stages of the curing process. © 2002 Society of Chemical Industry