The effect of kevlar fiber reinforcement on the curing,thermal, and dynamic‐mechanical properties of an epoxy/anhydride system

Curing, thermal, and dynamic‐mechanical relaxational behavior of an epoxy/‐anhydride resin and a Kevlar‐fiber/epoxy composite were compared. Reinforcement by Kevlar fibers had a catalytic effect on the curing reaction. Reinforced formulations produced higher extents of reaction than neat formulations at the same curing time. Curing kinetics was also studied by means of DSC heating scans. When the Kevlar content increased, the heat flow curves and the exothermic peak temperature shifted significantly to lower temperatures. The glass transition temperature of the matrix also decreased as the Kevlar content increased. Postcuring reduced the differences between the neat and reinforced formulations. Loss tangent and storage modulus versus frequency master curves were obtained from isothermal dynamic‐mechanical measurements. The effect of fiber addition on the main dynamic‐mechanical relaxation was analyzed with a simple mechanical model.     

Study of Hybridized Kenaf/Palf-Reinforced Hdpe Composites by Dynamic Mechanical Analysis

This article presents an experimental study on the dynamic mechanical property of hybridized Kenaf/PALF-reinforced HDPE composites. Variation in storage modulus (E′), loss modulus (E″) and damping parameter (tan δ) with fiber loading and variation in fiber length were investigated. The concept of hybridization was also discussed as it affects the dynamic properties. Initial storage modulus (E′) of all hybrids at different fibre ratios have been enormously improved compared to pure HDPE, and dependence of modulus on cellulose content of natural fibres was very clear. A lower percentage of PALF is required for hybridization with kenaf bast fibre to achieve a positive hybridization effect. Adequate hybridization could impart higher impact strength to the composite. The dynamic modulus curve showed an increase in the E′ value with increase in operating temperature up to about 130°C and is at a maximum at higher fibre loading. At lower temperatures, 60% of fibre loading had reduced the loss modulus peak of the pure HDPE. At temperature range of 30 to 65°C, incorporation of the fibres helped reduce the E″ peak of the matrix. Increasing the fibre content of the hybrids raised the damping peak with temperature. In addition, there is an increase in storage modulus with increased fibre length at room temperature up to about 65°C. Above this temperature, variation in fibre length became irrelevant up to the less viscous point of the matrix. A marginal difference in loss modulus with variation in fibre length was observed, no difference could be seen in the case of loss tangent (tan delta) in regard to variation in fibre length.     

Influence of fibre content on the strength of carbon fibre reinforced HfC/SiC composites up to 2100 °C

The influence of carbon fibre content on the mechanical behaviour of HfC/SiC composites was investigated up to 2100 °C for specimens containing 40 or 55 vol% fibres. Silicon carbide was added as a sintering aid during hot pressing. Increasing the fibre content made infiltration more difficult, which resulted in higher porosity in the specimen with 55 vol% fibres. The room temperature flexural strength ranged from 340 to 380 MPa, and it increased to more than 400 MPa at 1800 °C due to stress relaxation. Increasing temperature was accompanied by a decrease in the slope of the load-displacement curve, indicating a decrease in elastic modulus, but plastic deformation was not observed below 2100 °C. At 2100 °C, the specimen containing a higher fibre content underwent significant deformation due to low interfacial strength between the fibre plies, retaining a strength at the proportional limit of 290 MPa and an ultimate strength of 520 MPa.     

The rheological behavior and dynamic mechanical properties of syndiotactic 1,2‐polybutadiene

The rheological behavior and the dynamic mechanical properties of syndiotactic 1,2‐polybutadiene (sPB) were investigated by a rotational rheometer (MCR‐300) and a dynamic mechanical analyzer (DMA‐242C). Rheological behavior of sPB‐830, a sPB with crystalline degree of 20.1% and syndiotactic content of 65.1%, showed that storage modulus (G′) and loss modulus (G″) decreased, and the zero shear viscosity (η₀) decreased slightly with increasing temperature when measuring temperatures were lower than 160°C. However, G′ and G″ increased at the end region of relaxation curves with increasing temperature and η₀ increased with increasing temperature as the measuring temperatures were higher than 160°C. Furthermore, critical crosslinked reaction temperature was detected at about 160°C for sPB‐830. The crosslinked reaction was not detected when test temperature was lower than 150°C for measuring the dynamic mechanical properties of sample. The relationship between processing temperature and crosslinked reaction was proposed for the sPB‐830 sample. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Semi‐interpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. II. Dielectric relaxation and thermal behaviour

Semi‐interpenetrating polymer networks (semi‐IPNs) based on crosslinked polyurethane (PU) and linear polyvinylpyrrolidone (PVP) were synthezised, and their thermal and dynamic mechanical properties and dielectric relaxation behavior were studied to provide insight into their structure, especially according to their composition. The differential scanning calorimetry results showed the glass transitions of the pure components: one glass‐transition temperature (T_g) for PU and two transitions for PVP. Such glass transitions were also present in the semi‐IPNs, whatever their composition. The viscoelastic properties of the semi‐IPNs reflected their thermal behavior; it was shown that the semi‐IPNs presented three distinct dynamic mechanical relaxations related to these three T_g values. Although the temperature position of the PU maximum tan δ of the α‐relaxation was invariable, on the contrary the situation for the two maxima observed for PVP was more complex. Only the maximum of the highest temperature relaxation was shifted to lower temperatures with decreasing PVP content in the semi‐IPNs. In this study, we investigated the molecular mobility of the IPNs by means of dielectric relaxation spectroscopy; six relaxation processes were observed and indexed according the increase in the temperature range: the secondary β‐relaxations related to PU and PVP chains, an α‐relaxation due to the glass–rubber transition of the PU component, two α‐relaxations associated to the glass–rubber transitions of the PVP material, and an ionic conductivity relaxation due to the space charge polarization of PU. The temperature position of the α‐relaxation of PU was invariable in semi‐IPNs, as observed dynamic mechanical analysis measurements. However, the upper α‐relaxation process of PVP shifted to higher temperatures with increasing PVP content in the semi‐IPNs. We concluded that the investigated semi‐IPNs were two‐phase systems with incomplete phase separation and that the content of PVP in the IPNs governed the structure and corresponding properties of such systems through physical interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1191–1201, 2003     

Improvement in compression performance of the polysulfide sealant by thiol‐acrylate reaction

Trimethylolpropanetriacrylate (TMPTA) was added to the polysulfide‐manganese dioxide (PSF‐MnO₂) liquid mixtures as a crosslinker to improve their crosslinking capability. The samples were cured at room temperature for different times and the crosslinking degree was characterized by extraction and swelling tests. Mechanical properties of the cured samples including tensile, compression (stress relaxation, permanent set, and cyclic compression), and dynamic mechanical behaviors were investigated. The results indicated that the TMPTA crosslinker significantly increased the crosslinking degree and the homogeneity of the formed PSF networks. As a result, the tensile and compression stress and relaxation performances of the cured PSF rubber were dramatically improved. This result was also consistent with the results from the swelling, cyclic compression, and dynamic mechanical measurements. Interestingly, the tensile strength of the TMPTA cured samples did not show apparent change when the curing time was longer than 14 days, whereas their compression stress and relaxation performance were growing remarkably from 14 to 60 days. The improved performances were attributed to the high efficiency of thiol‐acrylate Michael addition reaction for the crosslinking. It promoted the curing rate, resulting in good compression properties in a much shorter curing time.POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Impact response of epoxy systems containing short fibres and/or oxide particles as reinforcements

This work looks at the role played by constant levels of fibre and/or particles in epoxy matrices on impact responses during dynamic loading. In order to delineate the differing roles of reinforcements, hybrid composites containing different amounts of fibres and particles were prepared. Maximum loads and energies were used to distinguish the responses during and following impact. Scanning electron microscopy (SEM) was used to characterize the surface features before and after failure. Furthermore, such microscopic analyses were also employed to substantiate the deductions arrived at based on mechanical data analysis, which included the deduced parameter in the form of energy for propagation. The experimental results pointed to the fact that the total energy and load generally rise as the fibre content in the epoxy system increases. The hybrids, on the other hand, displayed a trend where the normalized load and the total energy increased as the fibre content in the hybrid was raised from 1 to 5 vol%. This was most evident when the differing levels of fillers and fibres were fixed at a total of 7 vol%. In addition, comparison was made between two sets of compositions of fibres and particles in the composites. The results showed that the higher fibre content in the hybrid allowed greater load bearing and energy absorption and the difference in recorded levels increased with higher fibre content in one hybrid set. Fractography studies indicated flatter surface features for systems with only particles added, whereas the ‘all‐fibre’ bearing systems displayed ‘fast‐fracture’ features resembling ‘river patterns’. Copyright © 2004 Society of Chemical Industry     

Curing Kinetics and Effects of Fibre Surface Treatment and Curing Parameters on the Interfacial and Tensile Properties of Hemp/Epoxy Composites

The curing kinetics of neat epoxy (NE) and hemp fibre/epoxy composites was studied and assessed using two dynamic models (the Kissinger and Flynn–Wall–Ozawa Models) and an isothermal model (the Autocatalytic Model) which was generally supported by the experimental data obtained from dynamic and isothermal differential scanning calorimetry (DSC) scans. The activation energies for the curing of composites exhibited lower values compared to curing of NE which is believed to be due to higher nucleophilic activity of the amine groups of the curing agent in the presence of fibres. The highest tensile strength, σ was obtained with composites produced with an epoxy to curing agent ratio of 1:1 and the highest Young's modulus, E was obtained with an epoxy to curing agent ratio of 1:1.2. Alkali treated hemp fibre/epoxy (ATFE) composites were found to have higher σ and E values compared to those for untreated hemp fibre/epoxy (UTFE) composites which was consistent with the trend for interfacial shear strength (IFSS) values. Composites σ and E were found to be higher for a processing temperature of 70°C than for 25°C for both UTFE and ATFE composites, but were found to decrease as the curing temperature was increased further to 120°C.     

Phase separation,cure kinetics,and morphology of epoxy/poly(vinyl acetate) blends

Epoxy based on diglycidyl ether of bisphenol A + 4,4′diaminodiphenylsulfone blended with poly(vinyl acetate) (PVAc) was investigated through differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and environmental scanning electron microscopy (ESEM). The influence of PVAc content on reaction induced phase separation, cure kinetics, morphology and dynamic‐mechanical properties of cured blends at 180°C is reported. Epoxy/PVAc blends (5, 10 and 15 wt % of PVAc content) are initially miscible but phase separate upon curing. DMTA α‐relaxations of cured blends agree with T_g results by DSC. The conversion‐time data revealed the cure reaction was slower in the blends than in the neat system, although the autocatalytic cure mechanism was not affected by the addition of PVAc. ESEM showed the cured epoxy/PVAc blends had different morphologies as a function of PVAc content: an inversion in morphology took place for blends containing 15 wt % PVAc. The changes in the blend morphology with PVAc content had a clear effect on the DMTA behavior. Inverted morphology blends had low storage modulus values and a high capability to dissipate energy at temperatures higher than the PVAc glass‐transition temperature, in contrast to the behavior of neat epoxy and blends with a low PVAc content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1507–1516, 2007     

Gradient curing process in the mixed epoxy system and property analysis of the cured products

To improve the high-temperature mechanical properties of room temperature cured epoxy resin, a mixed curing agent was used and the curing process was studied under a temperature ramp. The tests including gelation time, differential scanning calorimetry, dynamic thermomechanical analysis, and flexural strength were taken to evaluate the changes in pot life, reaction process, heat resistance, and mechanical properties, respectively. The analysis then focused on the extent of cure. Meanwhile, the effects of non-reactive diluent on the curing process and product properties were analyzed. Results showed that the resin system containing the mixed curing agent possessed an exquisite characteristic when the temperature rose slowly to 363 or 393 K. The system could be preliminarily solidified in an hour and a half at normal temperature, and then in the heating-up environment, curing reactions initiated by different types of curing agents took place, caused the curing degree to exhibit certain gradient and increase to greater than 95% quickly. The glass transition temperature and the mechanical stability at high testing temperatures of the cured products were therefore improved. When dibutyl sebacate was added into the system as the diluent, the curing reaction was postponed, the curing degree was slightly increased; however, the glass transition temperature and mechanical properties at high temperatures were apparently decreased.     

Exploring a novel cyclic monofunctional peroxide for curing of silicone rubber at elevated temperature

The curing characteristics of silicone rubber (polydimethylsiloxane [PDMS]) in the presence of structurally different peroxides, namely dicumyl peroxide (DCP) and 3,3,5,7,7‐pentamethyl‐1,2,4‐trioxepane (PMTO), have been studied in details. At moderate temperature, DCP is more prominent for curing the silicone rubber but at high temperatures it suffers from low scorch safety. An inhibitor 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO) was added with DCP to stabilize the radicals in order to increase the scorch safety time. On the other hand, PMTO showed a prolonged scorch safety and better crosslinking efficiency rather than (DCP + TEMPO) mix at higher temperatures. PMTO‐crosslinked PDMS shows better crosslinking efficiency as indicated by a higher gel content and low swelling index value. Also the mechanical properties, thermal stability, and dynamic mechanical behavior of PMTO‐crosslinked PDMS are much superior than (DCP + TEMPO)‐crosslinked PDMS. Apart from thermoplastic vulcanizates (TPVs) made from PMTO‐crosslinked PDMS show better physicomechanical behavior compared to the TPVs made from (DCP + TEMPO)‐crosslinked PDMS. Moreover, DCP undergoes decomposition reactions at a higher temperature and forms acetophenone, which leads to an unpleasant smell in the final products whereas no such phenomenon is observed for PMTO. Therefore, PMTO turns out to be the suitable peroxide for crosslinking of PDMS at higher temperature. POLYM. ENG. SCI., 57:1073–1082, 2017. © 2016 Society of Plastics Engineers     

Untersuchungen zum Schmelz- und Strukturverhalten von Polyethylenterephthalatfasern in Luft bei 1 bar und in überkritischem CO2 bis 280 bar

A comparative study was carried out as to the influence of CO₂ on changes of the fibre structure of thermofixed and unfixed PETP multifilament and monofilament fibres in relation to pressure and temperature. To this aim measurements were carried out on the glass transition-, the pre-melting- and the melting temperature with a dynamic heat flow difference calorimeter (DDC) in air at 1 bar, as well as in CO₂ at pressures up to 280 bar. In the thermograms taken under high pressure the melting point was clearly visible, in contrast to the glass transition- and pre-melting temperatures. Owing to its hydrophobic properties, the CO₂ is capable of diffusing into the fibre where it can act as a virtual contamination to the effect that the melting point at 280 bar is lowered by 13–14°C for all PETP fibres. Measurements of the pre-melting temperature, stress-strain behaviour and shrinkage after treatment of the PETP fibres at temperatures between 80 and 200°C in air and CO₂ show that particularly in the case of non-thermofixed PETP yarns at 280 bar structural changes are brought about from temperatures as low as 80°C upwards which are attributable to partial crystallite growth in the imperfect areas of the fibre polymers. In CO₂ at 280 bar, this results in higher pre-melting temperatures, increased shrinkage and higher elasticity of the fibres in contrast to air at 1 bar at comparable treatment temperatures. In the case of thermofixed fibres these effects are, as a rule, considerably less marked.     

Reaction kinetics and thermal properties of cyanate ester‐cured epoxy resin with phenolphthalein poly(ether ketone)

This article describe the influence of phenolphthalein poly (ether ketone) (PEK‐C) on the cure behaviors and thermal properties of the diglycidyl ether of bisphenol A (DGEBA) epoxy resin with cyanate ester as curing agent. The curing kinetics and reaction pathways were monitored using dynamic differential scanning calorimeter and Fourier transform infrared spectroscopy. The dependence of activation energy on the conversion degree for all the studied systems was calculated in the light of Ozawa‐Flynn‐Wall method. Furthermore, the thermomechanical properties and the thermal stability of the cured resins were also evaluated by dynamic mechanical analysis and thermogravimetric analysis, respectively. Conclusions can be drawn as follows: the main reaction pathways did not vary with the inclusion of PEK‐C, but the reaction rate of the blend was found to be higher than that of the neat epoxy. The glass transition temperature of the blend was not changed by the addition of PEK‐C, while the initial decomposition temperature slightly decreased with increase in PEK‐C content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Free radical activity in gamma‐irradiated polyethylene film,drawn tape and ultra‐high‐modulus fibres determined by grafting performance

Grafting rates of gaseous butadiene to a range of morphological forms of gamma‐irradiated polyethylene, including ultra‐high‐modulus fibres (UHMPE), have been measured in order to determine the availability of active free radicals over time at various temperatures. Blank experiments on unirradiated samples showed that monomer diffusion is not rate‐controlling with film and natural draw ratio tapes, but is likely to be a major factor in the control of grafting rates in UHMPE fibres. Grafting rates from monomer loss/time experiments with irradiated samples indicate that grafting is always in competition with free radical self‐annihilation, the extent being influenced by temperature, dose and morphology, including prior sample annealing. At lower temperatures, graft‐active radicals are produced over long periods of time, eg close to linear grafting rates were monitored over 20 hours for PE tape at 0 °C (50 kGy) and for gel‐spun UHMPE at 40 °C (100 kGy). At higher temperatures, grafting rates steadily decrease with time. Grafting rates are almost independent of irradiation dose in the early stages, however, the dose has an increasing positive influence as the reaction proceeds. At any given temperature and irradiation dose, the rates decrease in the series undrawn film; natural draw ratio tape; high draw ratio gel‐spun fibre; high draw ratio melt‐spun fibre. An analogy is drawn between these results and the optimum conditions required for improving the creep properties of PE tape and UHMPE fibres by acetylene‐sensitized irradiation crosslinking. Copyright © 2005 Society of Chemical Industry     

Biobased epoxy resin from canola oil

Epoxidized canola oil (ECO)‐based thermoset epoxy resins were formulated with phthalic anhydride (PA) as the curing agent for different ratios of ECO to PA (1:1, 1:1.5, and 1:2 mol/mol) at curing temperatures of 155, 170, 185, and 200°C. The gelation process of the epoxy resins and the viscoelastic properties of the systems during curing were studied by rheometry, whereas the dynamic mechanical and thermal properties of the cured resins were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry. We found that the thermomechanical properties of the resins were not strongly dependent on the curing temperature of the resin, although elevated temperatures significantly accelerated the curing process. However, an increase in the curing agent (PA) amount significantly altered both the reaction rate and the thermomechanical properties of the final resin. Thus, in the ECO/PA system, the selection of the combination of the curing temperature and the molar ratios of the curing agent could be used to design thermoset resins with unique thermomechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40142.     

Determination of the strain characteristics of synthetic fibres in variable temperature conditions

It was shown that the mean statistical relaxation and lag time functions and transformations of the graphs of these functions (turning by angles that are linearly dependent on the temperature) totally determine the values of the relaxation and lag times of PET fibre at variable temperatures. The asymptotic values of the relaxation modulus and ductility and the structural parameters of the intensity of relaxation and creep of PET fibre are a linear function of the temperature in a first approximation. The reported methods of determining the strain characteristics of fibres at variable temperatures can be used to predict thermoviscoelastic processes. __________ Translated from Khimicheskie Volokna, No. 3, pp. 58–60, May–June, 2006.     

Rheological cure characterization of phosphazene–triazine polymers

Cyclomatrix phosphazene–triazine network polymers were synthesized by co‐curing a blend of tris(2‐allylphenoxy), triphenoxy cyclotriphosphazene (TAP), and tris(2‐allylphenoxy) s‐triazine (TAT) with bis(4‐maleimido phenyl) methane (BMM). The co‐curing of the three‐component resin was investigated by dynamic mechanical analysis using rheometry. The cure kinetics of the Diels–Alder step was studied by examining the evolution of the rheological parameters, such as storage modulus (G′), loss modulus (G″), and complex viscosity (η*), for resins of varying compositions at different temperatures. The curing conformed to an overall second‐order phenomenological equation, taking into account a self‐acceleration effect. The kinetic parameters were evaluated by multiple‐regression analysis. The absence of a definite trend in the cure process with blend composition ratio was attributed to the occurrence of a multitude of competitive reactions whose relative rates depend on the reactant ratio and the concentration of the products formed from the initial phase of reaction. The cure was accelerated by temperature for a given composition, whereas the self‐acceleration became less prominent at higher temperature. Gelation was accelerated by temperature. The gel conversion decreased with increase in maleimide concentration and, for a given composition, it was independent of the cure temperature. The activation energy for the initial reaction and the crosslinking process were estimated for a composition with a maleimide‐to‐allyl ratio of 2 : 1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 908–914, 2003     

Geometrical range of microscopic stress distribution change due to fibre array irregularities for thermally and transversely loaded CF/epoxy composites

Abstract

A detailed numerical investigation has been carried out to investigate the effect of local fibre array irregularities on microscopic interfacial normal stress for transversely loaded unidirectional carbon fibre/epoxy composites with random fibre arrangement. Linear elastic finite element analyses were carried out for a two-dimensional image based model composed of 70 fibres. One fibre in this image based model is replaced with resin as the resin equivalent fibre, and the resulting change in microscopic interfacial normal stress distribution is investigated. Three fibres are selected for the resin equivalent fibres to clarify the individual local geometrical irregularity. Calculations were carried out for three loading conditions: case A, cooling of –155 K from the curing temperature; case B, transverse loading of 75 MPa chosen as an example of macroscopic transverse fracture strength and case C, both cooling from the curing temperature and transverse loading of 75 MPa. The effect of fibre array irregularities on the interfacial stress state is limited to the region between the resin equivalent fibre and its first neighbouring fibres. The contribution of the second neighbouring fibre is small and that of further fibres is negligible.     

Cure kinetics and physical properties of dicyanate/polyetherimide semi‐IPNs

The curing behavior and physical properties of dicyanate/polyetherimide (PEI) semi‐interpenetrating polymer network (IPN) systems were investigated. Differential scanning calorimetry (DSC) was used to study the curing behavior of the dicyanate/PEI semi‐IPN systems. The curing rate of the semi‐IPN system decreased as the PEI content increased. An autocatalytic reaction mechanism can describe well the curing kinetics of the semi‐IPN systems. The reaction kinetic parameters were determined by fitting DSC conversion data to the kinetic equation. The glass transition temperature of the semi‐IPNs decreased with increasing PEI content. Two glass transitions due to phase‐separated morphology were observed for the semi‐IPN containing over 15 phr (parts per hundred parts of dicyanate resin) PEI. The thermal stability and dynamic mechanical properties of the semi‐IPNs were measured by thermal analysis.     

Curing behavior and dielectric properties of hyperbranched poly(phenylene oxide)/cyanate ester resins

A novel hyperbranched poly(phenylene oxide) (HBPPO) modified 2,2′‐bis(4‐cyanatophenyl) isopropylidene (BCE) resin system with significantly reduced curing temperature and outstanding dielectric properties was developed, and the effect of the content of HBPPO on the curing behavior and dielectric properties as well as their origins was thoroughly investigated. Results show that BCE/HBPPO has significantly lower curing temperature than BCE owing to the different curing mechanisms between the two systems, the difference also brings different crosslinked networks and thus dielectric properties. The dielectric properties are frequency and temperature dependence, which are closely related with the content of HBPPO in the BCE/HBPPO system. BCE/2.5 HBPPO and BCE/5 HBPPO resins have lower dielectric constant than BCE resin over the whole frequency range tested, while BCE/10 HBPPO resin exhibits higher dielectric constant than BCE resin in the low frequency range (<10⁴ Hz) at 200°C. At 150°C or higher temperature, the dielectric loss at the frequency lower than 10² Hz becomes sensitive to the content of HBPPO. These phenomena can be attributed to the molecular relaxation. Two relaxation processes (α‐ and β‐relaxation processes) are observed. The β‐relaxation process shifts toward higher frequency with the increase of temperature because of the polymer structure and chain flexibility; the α‐relaxation process appears at high temperature resulting from the chain‐mobility effects. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011