Viscoelastic properties and morphology of dicyanate ester/epoxy co-polymers modified with polysiloxane and butadiene–acrylonitrile rubbers

Dynamic mechanical analysis was conducted on specimens prepared from cyanate ester (CE) and epoxy (EP) resins cured together at various mass compositions. Increase of amount of epoxy resin in composition was shown to have a disadvantageous effect on glass transition temperature (T _g). It was shown that post-curing procedure was needed to produce a polymer matrix with a single glass transition relaxation, but increase in post-cure temperature up to 250 °C resulted in slight reduction in T _g for epoxy/cyanate copolymers. TG results proved that the presence of epoxy resin reduces thermal stability of the cyanate/epoxy materials. The neat CE and EP/CE systems containing 30 wt% of epoxy resin were modified using epoxy-terminated butadiene–acrylonitrile rubber (ETBN) and polysiloxane core–shell elastomer (PS). The scanning electron microscopy (SEM) results showed the existence of second phase of ETBN and PS modifiers. Only in the case of EP/CE composition modified with ETBN, well-dispersed second phase domains were observed. Analysis of SEM images for other CE- and EP/CE-modified systems revealed the formation of spherical aggregates.     

Combined effect of zeolite and boric acid on thermal behavior of epoxy composites

The particles of natural zeolite in combination with boric acid were incorporated into the epoxy resin ED-20 in order to improve the thermal stability of epoxy polymer. Epoxy resin was cured using polyethylenepolyamine. Characterization of the epoxy composites was carried out by using Fourier transform infrared spectrometry, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) under flow of air and argon. The thermal behavior of the zeolite/boric acid-based epoxy composites (total percentage 15 mass%) were compared with that of 15 mass% boric acid-based epoxy system and the neat epoxy resin. TG and DSC results revealed that the combination of 5 mass% zeolite and 10 mass% boric acid significantly increased the mid-point temperature and residue, and decreased the maximum decomposition rate of the epoxy composites at the heating.     

Kinetics of curing and thermal degradation of hyperbranched epoxy (HTDE)/diglycidyl ether of bisphenol-A epoxy hybrid resin

Hyperbranched epoxy resin (HTDE) has relatively low viscosity and high molecular mass and holds great promise as a functional additive for enhancing the strength and toughness of thermosetting resins. In this work, the curing and thermal degradation kinetics of HTDE/diglycidyl ether of bisphenol-A epoxy (DGEBA) hybrid resin were studied in detail using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) techniques by Coats–Redfern model. The effect of molecular mass or generation and content of HTME on the activation energy, reaction order, and curing time were discussed; the results indicated that HTDE could accelerate the curing speed and reduce the activation energy and reaction order of the curing reaction.     

Influence of the network chain orientation on the fracture toughness of a mesogenic epoxy resin modified with CTBN

A biphenol‐type epoxy resin, which had a mesogenic group in the backbone moiety, was modified with carboxy‐terminated butadiene acrylonitrile copolymer (CTBN) as a reactive elastomer, and its fracture toughness was measured. With the addition of CTBN, the fracture toughness of the biphenol‐type epoxy resin significantly increased and became significantly higher than that of a bisphenol A‐type epoxy resin modified with CTBN. The network chain orientation in the cured biphenol‐type epoxy resin system was clearly observed during the fracture process with polarized microscopy Fourier transform infrared measurements, although such a phenomenon was not observed in the bisphenol A‐type epoxy resin system. The high toughness of the cured biphenol‐type system was clearly due to the consumption of the mechanical energy by a large deformation of the matrix resin due to the orientation of the network chains during the fracture process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1198–1209, 2003     

Synthesis,characterization, processability,mechanical properties,flame retardant,and oil resistance of chlorinated acrylonitrile butadiene rubber

Novel chlorinated acrylonitrile butadiene rubber (Cl‐NBR) was prepared from NBR by the alkaline hydrolysis of chloroform by using phase‐transfer catalysis. The formation of Cl‐NBR was monitored by ¹H‐NMR, UV‐Vis, and Fourier transform infrared spectroscopic techniques. The percentage of chlorine attached to the rubber chain was estimated by Volhard method. The effect of polar groups on the structural and thermal properties of Cl‐NBR was analyzed by scanning electron microscopy, X‐ray diffraction analysis, differential scanning calorimetry, and thermogravimetric analysis studies. The flame retardant, oil resistance, cure behavior, and mechanical properties of chlorinated elastomer were also analyzed. The proton NMR revealed the attachment of chlorine in the backbone of NBR with new chemical shift values. The C‐Cl stretching of chlorinated NBR was confirmed from Fourier transform infrared. The UV spectrum also supported the formation of chlorinated unit in the NBR chain through the shifts and broadening of absorption peaks. The X‐ray diffraction analysis pattern indicated a decrease in the amorphous domain of NBR with an increase in the level of chemical modification. The increased glass transition temperature obtained from differential scanning calorimetry confirms the increased molecular rigidity of the chlorinated NBR and thermal transitions increased with increase in the level of chemical modification. The thermal stability of Cl‐NBR decreased with an increase in chlorine content. The flame and oil resistance of Cl‐NBR was greatly higher than pure NBR due to the increased polarity of modified rubber. The superior tensile strength of Cl‐NBR (4 times higher than pure NBR) and higher oil resistance find applications in pump diaphragms, aircraft hoses, oil‐lined tubing, and gaskets materials with the excellent flame resistant property.     

Synthesis and properties of Fe0.83V1.17O4

Thermal properties of the organic–inorganic bicontinuous nanocomposites prepared via in situ two-stage polymerization of various silanes, epoxy, and amine monomers are investigated, and the impact of filler content and its organic compatibility on thermal stability of these nanocomposites is studied. Two series of epoxy–silica nanocomposites, namely, EpSi-A and EpSi-B containing 0–20 wt% silica, are synthesized. An epoxy–silane coupling agent is employed to improve the organic compatibility of silica in EpSi–B nanocomposites. The composites synthesized via two-stage polymerization are characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. DSC and TG/differential thermogravimetric results reveal substantially high glass transition (T _g) and excellent thermal stability of the bicontinuous nanocomposites as compared with pristine epoxy polymer. Both T _g and thermal properties, however, considerably vary depending on the organic compatibility of the nanocomposites. Significantly higher decomposition temperatures are recorded in case of EpSi-B nanocomposites owing to the chemical links between the epoxy and silica phases. Kinetic studies also show relatively higher activation energies of pyrolysis for EpSi-B nanocomposites.     

Thermal stability of acrylonitrile/chlorosulphonated polyethylene rubber blend

The properties of chlorosulphonated polyethylene (CSM) rubber, acrylonitrile rubber (NBR) and their blend (50/50 w/w) were studied. Fourier transform infrared (FTIR) studies supported that CSM/NBR rubber blend is self curable, when cross-linking takes place between acrylonitrile groups of NBR and –SO₂Cl groups or in situ generated allyl chloride moieties of CSM. The thermal stability of vulcanizates was analyzed in nitrogen by thermogravimetry. It was found that the initial degradation temperature of elastomer based on CSM rubber is lower than of pure NBR rubber. By adding NBR to CSM rubbers, the degradation temperature of crosslinked material increased, indicating higher thermal stability. The activation energy for the degradation are determined using the Arrhenius equation The activation energies for the rubber blends are higher than for elastomers based on pure rubbers. It was found that the mass loss of the blends at any temperature was between those of the pure rubbers. The differential scanning calorimetry (DSC) was used for the glass transition temperature determination. It is estimated thermodynamic immiscibility of NBR/CSM blend based on noticed two different glass transition temperatures, corresponding to CSM and NBR rubbers.     

Analysis of structure–properties relationship in nitrile‐butadiene rubber/phenolic resin/organoclay ternary nanocomposites using simple model system

The present study deals with the structure–property relationship of organoclay (OC) filled nanocomposites based on rubber blend comprising of nitrile‐butadiene rubber (NBR) and phenolic resin (PH). To obtain a better insight into the characteristics of the NBR/PH/OC hybrid system, a simple model system consisting of NBR/OC nanocomposites is also taken into consideration. A series of NBR/OC and NBR/PH/OC nanocomposites containing a wide range of OC concentrations (2.5–30 phr) are prepared by using traditional open two‐roll mill. Structural analysis performed by X‐ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM) exhibits mixed exfoliated and intercalated morphology at low OC content, below 7.5 phr, and a well‐ordered intercalated morphology at higher OC loading. It is shown that the dispersion of OC is also influenced by mixing time and order of mixing of components. Analysis of the cure characteristics, mechanical, and thermal properties of both the NBR/OC and NBR/PH/OC nanocomposites reveals that the OC is dispersed mainly in the NBR continuous phase, even though some is likely localized in the rubber–resin interface. Copyright © 2009 John Wiley & Sons, Ltd.     

Processing and thermal properties evaluation of silylated apophyllite–filled epoxy nanocomposite

The primary objective of the research was to evaluate the rheology and thermal properties of silylated apophyllite–filled epoxy nanocomposite. Several n‐octyldimethylsiloxy‐apophyllite with different grafting degrees were synthesized by controlling the ratio of the apophyllite and n‐octyldimethylchlorosilane. The thermal studies of silylated apophyllite have shown that the onset decomposition temperature of silylated apophyllite far exceeds the onset temperature of conventional organoclays (~260 °C). Chemorheological measurements of 1.8 wt% silylated apophyllite–filled tetra functional epoxy (MY720) and difunctional epoxy (DER661) resin mixture showed that the addition of the silylated apophyllite does not dramatically affect the cure profile of the epoxy resin with the availability of 40 min of processing window after the addition of apophyllite. Wide angle X‐ray diffraction and transmission electron microscopy results of the shear mixed and cured nanocomposite suggest that the apophyllite was well dispersed in the epoxy matrix. The thermal studies of epoxy nanocomposite showed an increase in the char yield on the addition of silylated apophyllite to the epoxy resin. In addition, an improvement in the onset decomposition temperature of the cyanopropyldimethylsiloxy‐apophyllite epoxy nanocomposite was observed compared with that of pure epoxy resin. Copyright © 2011 John Wiley & Sons, Ltd.     

双酚A在环氧树脂和端羧丁腈增韧的环氧树脂中作用的研究

本文分别以六氢吡啶、三乙醇胺、70~#酸酐和三氟化硼单乙胺络合物为固化剂,研究了用双酚A改性的环氧树脂和端羧丁腈(简称CTBN)增韧的环氧树脂体系的热、机械性能、微观形貌和交联密度。研究结果表明只有在碱性催化型固化剂六氢吡啶或三乙醇胺下,双酚A的加入才会有突出的增韧效果。结果指出固化物冲击韧性的提高与网络交联密度有关,断裂韧性的提高是析出橡胶相体积分数增大和基体交联密度减小的协同作用所致。     

Enhanced fracture toughness and mechanical properties of epoxy resin with rice husk-based nano-silica

This paper reports a novel approach to toughen epoxy resin with nano-silica fabricated from rice husk using a thermal treatment method with a particle size distribution in range of 40–80 nm. The nano-silica content was in the range, 0.03–0.10 phr, with respect to epoxy. The mechanical test showed that with the addition of 0.07 phr of rice husk based nano-silica, the fracture toughness of the neat epoxy resin increased 16.3% from 0.61 to 0.71 MPa m^1/2. The dynamic mechanical analysis test results showed that the glass transition temperature (T _g) of a 0.07 phr nano-silica dispersion in epoxy resin shifted to a higher temperature from 140 to 147°C compared to neat epoxy resin. SEM further showed that the nano-silica particles dispersed throughout the epoxy resin prevented and altered the path of crack growth along with a change in the fracture surface morphology of cured epoxy resin.     

Fracture toughening of epoxy matrices with blends of resins of different molecular weights and other modifiers

The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004     

Thermal properties and combustibility of elastomer–protein composites

This article presents the test results of thermal properties and flammability of crosslinked nitrile rubber in the presence of zinc oxide or nano-zinc oxide containing waste keratin, using the test results obtained by means of a derivatograph, DSC, and oxygen index. The influence of modified montmorillonite (NanoBent) on selected properties of investigated elastomer–protein composites has also been studied. The composites' thermal stability and flammability depend on the method of composite preparation and the quantity of added keratin. The addition of waste keratin reduces the flammability of NBR–keratin composites.     

Thermal Analysis of Polymer-silicate Nanocomposites

The thermal behavior of epoxy-smectite nanocomposites (hybrids) is examined by non-isothermal thermogravimetry (TG, DTG and DTA) in air atmosphere. It has been shown that the thermal stability of hybrids is much greater than that of epoxy resin and strongly depends on both the smectite loading and the type of the gallery cations of organically modified smectites. The kinetics of degradation of nanocomposites is significantly influenced by the presence of smectites and proceeds in three stages. Stage I is attributed to the effect of quaternized ammonium ion exchanged smectite, as stages II and III are associated with the decomposition of the bulk epoxy resin. Because of the interfacial interactions and thesilicate-polymer multilayered nanoscale organization, the nanocomposites act as excellent heat insulator and mass transport barrier, which shift the thermal decomposition peaks towards much higher temperatures. This revised version was published online in July 2006 with corrections to the Cover Date.     

Toughening behavior of polyamide-rubber blends

The impact behavior of nylon 6- rubber blends is studied by varying the rubber concentration (0–26 vol. %), rubber particle size (0.1 - 2.0 μm) and rubber properties. The brittle to tough transition shifts to lower temperatures by increasing the rubber concentration, decreasing the particle size and by lowering the modulus of the elastomer. With very small particle sizes, however, the transition temperature increases again. The toughness of the blends above their transition temperature increases with the rubber concentration, but the particle size has only some effect. Very small particle sizes decrease the impact behavior. The postulated deformation mechanism is cavitation of the rubber followed by shear deformation of the matrix.     

弹性体增韧环氧树脂研究进展

聚氨酯和丁腈橡胶是两种对环氧树脂增韧效果显著的橡胶弹性体,文章分别介绍了这两种弹性体增韧改性环氧树脂的机理和近年来的主要研究进展,并讨论了聚氨酯增韧环氧树脂和丁腈橡胶增韧环氧树脂各自的特点,展望了弹性体增韧环氧树脂的前景。     

Influence of cryogenic modification of silica on thermal properties and flammability of cross-linked nitrile rubber

The article presents the results of testing thermal properties and combustibility of butadieneacrylonitrile rubber with 18% contents of bounded acrylonitrile, NBR 18. Two types of silica, Zeosil 175C and Ultrasil VN-3, with different specific surfaces were used as filler. Zeosil 175C and Ultrasil VN-3 were modified via cryogenic dezaggregation method. The activity of unmodified and cryogenic modified silica toward butadiene-acrylonitrile rubber were investigated. The sulphur and peroxide vulcanizates contained 20, 30, 40, and 50 phr. of the filler were studied. The article discusses also the test results of thermal stability and flammability of NBR 18 containing silica prepared "in situ" from alkoxysilane precursor. The test results were obtained with the use of derivatograph, measurements of flammability by the method of oxygen index, and in air. The effect of the silica modification on the SEM and AFM was also examined. The method of cryogenic modification enables to achieve increase of mineral fillers activity towards elastomer and reduction in the flammability of NBR 18 vulcanizates. It has been found that the modification of the vulcanizates of NBR 18 with tetraethoxysilane that makes it possible to form silica "in situ" reduces the flammability of cross-linked rubbers.     

High mechanical and thermal performance of Sasobit-modified epoxy resin,prepared via vacuum shock technique

In this study, thermal and mechanical properties of novel nanocomposite, epoxy resin reinforced with octadecylamine functionalized graphene oxide (GO-ODA) and Sasobit, prepared via creative vacuum shock technique, were investigated. By introducing 1, 3 and 5 wt% Sasobit to the neat epoxy resin, the tensile strength increased remarkably by 104%, 315% and 266%, respectively due to the unique stiff and crystalline structure of Sasobit. In addition, considerable enhancement of 125% in Young's modulus, 351% in toughness, 562% in impact resistance, ~19 °C in thermal stability and ~7 °C in glass transition temperature of epoxy resin with 3 wt% Sasobit loading was demonstrated. The composite containing 3 wt% Sasobit alone, were found to have even superior properties than GO-ODA/epoxy nanocomposite, as surprisingly 3, 2.9, 2.2 and 2 times more improvement, respectively in tensile strength, toughness, impact strength and thermal stability of epoxy resin compared to reinforcement with GO-ODA were obtained.     

Studies on phase morphology and thermo-physical properties of nitrile rubber blends

The study deals with the morphological and thermal analysis of binary rubber blends of acrylonitrile-co-butadiene rubber (NBR) with another polymer. Either ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA), chlorosulphonated polyethylene (CSM), or polyvinyl chloride (PVC) has been selected for the second phase. Depending on the relative polarity and interaction parameter of the components, the binary blends showed development of a bi-phasic morphology through scanning electron microscopy (SEM). Use of different types of thermal analysis techniques revealed that these blends are generally incompatible excepting one of NBR and PVC. Derivative differential scanning calorimetry (DDSC), in place of conventional DSC, has been used to characterize the compatibility behavior of the blends. NBR–PVC shows appearance of only one glass transition temperature (T _g) averaging the individual T _g’s of the blend components. The partially missible blend of NBR and CSM shows a broadening of T _g interval between the phase components, while the immiscible blends of either NBR–EPDM or NBR–EVA do not show any change in T _g values corresponding to the individual rubbers of their blend. The experimental T _g values were also compared with those calculated theoretically by Fox equation and observed to match closely with each other. Studies have also been made to evaluate the thermal stability of these blends by thermo-gravimetric analysis (TG) and evaluation of activation energy of respective decomposition processes by Flynn and Wall method. Thermo-mechanical analysis (TMA) was found to be effective for comparison of creep recovery and dimensional stability of the blends both at sub-ambient as well as at elevated temperatures.     

Phase separation during synthesis of polyetherimide/epoxy semi-IPNs

The phase separation behavior and the morphology of polyetherimide (PEI)-modified diglycidyl ether of bisphenol A (DGEBA) epoxy resin were studied using scanning electron microscopy and light scattering. Reaction kinetics, cloud point and onset of gelation were determined by differential scanning calorimeter, optical microscope and physica rheometer, respectively. The mixture of partially cured epoxy and PEI showed bimodal upper critical solution temperature (UCST) behavior. For PEI content smaller than 10 wt%, the blends exhibited a sea-island morphology formed via nucleation and a growth mechanism. Above 25 wt% PEI content, the phase separation proceeded via a spinodal decomposition mechanism and a nodular structure was formed. With PEI content between 15 and 20 wt%, dual phase morphology was observed. This morphology was formed via primary spinodal decomposition and secondary phase separation within the dispersed phases and the matrix phases formed by the primary phase separation. This morphology was presumed to be formed in the reaction-induced phase separation mechanism with the mixture showing bimodal UCST behavior. The curing temperature had an effect on the final morphology, and the modulus of PEI-modified epoxy was influenced by the phase separation.