Curing behavior and thermal mechanical properties of cyanate ester blends

Cyanate esters are a class of important thermally resistant polymers. To tailor their processability and thermomechanical properties, a series of cyanate ester blends based on a trifunctional novolac cyanate ester (HF‐5), a difunctional bisphenol E cyanate ester (HF‐9), and a reactive catalyst [2,2′‐diallyl bisphenol A (DBA)] were formulated. The effect of the blend composition on the rheology and curing behavior of these cyanate ester blends and the corresponding thermal and mechanical properties of the cured cyanate ester blends was studied. The results showed that HF‐5 contributed to good mechanical property retention at high temperatures because of its trifunctionality, whereas HF‐9 imparted processability by reducing the viscosity and extending the pot life of the formulated cyanate ester blends at the processing temperature. On the basis of the results, an optimal cyanate ester blend suitable for resin transfer molding was determined: the HF‐5/HF‐9/DBA weight ratio of 80 : 15 : 5 exhibited good processability and thermomechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4284–4290, 2006     

Cure reaction and phase separation behavior of cyanate ester‐cured epoxy/polyphenylene oxide blends

The cure reaction and phase separation mechanism of a cyanate ester‐cured epoxy and its blends with polyphenylene oxide (PPO) were studied. An autocatalytic mechanism was observed for the epoxy and its blends. The reaction rate of the blends was higher than that of the neat epoxy at initial stage; however, the reached conversion decreased with PPO content. FTIR analysis revealed that the cyanate functional group reactions were accelerated by adding PPO and indicated that several coreactions have occurred. This was caused by the reaction of cyanate ester with the PPO reactive chain ends. But at a later stage of cure, the reaction could not progress further due to diffusional limitation of PPO. To understand the relationship between the cure kinetics and phase separation of the blends, the morphology of the blends during cure was examined. When the homogeneous epoxy/PPO blends with low PPO content (10 phr) were cured isothermally, the blends were separated by nucleation and growth (NG) mechanism to form the PPO particle structure. But at high PPO content (30 phr), the phase separation took place via spinodal decomposition (SD). SD is favored near critical concentration and high cure rate system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1139–1145, 2006     

Preparation and properties of halogen‐free flame‐retarded phthalonitrile–epoxy blends

Halogen‐free flame‐retarded blends composed of 2,2‐bis[4‐(3,4‐dicyanophenoxy) phenyl] propane (BAPh) and epoxy resin E‐44 (EP) were successfully prepared with 4,4′‐diaminodiphenyl sulfone as a curing additive. The structure of the copolymers was characterized by Fourier transform infrared spectroscopy, which showed that epoxy groups, a phthalocyanine ring, and a triazine ring existed. The limiting oxygen index values were over 30, and the UL‐94 rating reached V‐0 for the 20 : 80 (w/w) BAPh/EP copolymers. Differential scanning calorimetry and dynamic rheological analysis were employed to study the curing reaction behaviors of the phthalonitrile/epoxy blends. Also, the gelation time was shortened to 3 min when the prepolymerization temperature was 190°C. Thermogravimetric analysis showed that the thermal decomposition of the phthalonitrile/epoxy copolymers significantly improved with increasing BAPh content. The flexible strength of the 20:80 copolymers reached 149.5 MPa, which enhanced by 40 MPa compared to pure EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cure kinetics and thermal properties of tetramethylbiphenyl epoxy resin/phthalazinone‐containing diamine/hexa(phenoxy)cyclotriphophazene system

Inherently flame retardant epoxy resin is a kind of halogen‐free material for making high‐performance electronic materials. This work describes an inherently flame retardant epoxy system composed of 4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP), 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐(4‐(4‐aminophenoxy) phenyl) (2H) phthalazin‐1‐one (DAP), and hexa(phenoxy) cyclotriphophazene (HPCTP). The cure kinetics of TMBP/DAP in the presence or absence of HPCTP were investigated using isoconversional method by means of nonisothermal differential scanning calorimeter (DSC). Kinetic analysis results indicated that the effective activation energy (E_α) decreased with increasing the extent of conversion (α) for TMBP/DAP system because diffusion‐controlled reaction dominated the curing reaction gradually in the later cure stage. TMBP/DAP/HPCTP(10 wt %) system had higher E_α values than those of TMBP/DAP system in the early cure stage (α < 0.35), and an increase phenomenon of E_α ～ α dependence in the later cure stage (α ≥ 0.60) due to kinetic‐controlled reaction in the later cure stage. Such complex E_α ～ α dependence of TMBP/DAP/HPCTP(10 wt %) system might be associated with the change of the physical state (mainly viscosity) of the curing system due to the introduction of HPCTP. These cured epoxy resins had very high glass transition temperatures (202–235°C), excellent thermal stability with high 5 wt % decomposition temperatures (>340°C) and high char yields (>25.6 wt %). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical and thermal properties of poly(butylene succinate)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biodegradable blends

Biodegradable polymer blends of poly(butylene succinate) (PBS) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) were prepared with different compositions. The mechanical properties of the blends were studied through tensile testing and dynamic mechanical thermal analysis. The dependence of the elastic modulus and strength data on the blend composition was modeled on the basis of the equivalent box model. The fitting parameters indicated complete immiscibility between PBS and PHBV and a moderate adhesion level between them. The immiscibility of the parent phases was also evidenced by scanning electron observation of the prepared blends. The thermal properties of the blends were studied through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC results showed an enhancement of the crystallization behavior of PBS after it was blended with PHBV, whereas the thermal stability of PBS was reduced in the blends, as shown by the TGA thermograms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42815.     

Optimization of the thermal mending process in epoxy/cyclic olefin copolymer blends

Cyclic olefin copolymer (COC) is utilized as thermoplastic healing agent in an epoxy resin and the effect of mending temperature on the healing of resulting materials is investigated. Blends are prepared by adding 20 and 30 wt% COC powder in the epoxy resin. They are thermo-mechanically characterized and fractured samples are thermally mended at various temperatures to evaluate the healing efficiency of the repaired samples. Optical microscopy reveals a homogenous dispersion of COC domains within epoxy matrix, while thermogravimetric analysis shows improved thermal stability of the samples. The immiscibility of the two phases in the blends lead to a decrease of the mechanical properties under flexural and tensile loading modes with respect to neat epoxy. The fracture toughness increases upon COC addition at elevated amounts. Healing efficiency values up to more than 80% are obtained at the lowest investigated temperature of 145°C for samples with 30 wt% of COC.     

Characterization of the mechanical and thermal properties and morphological behavior of biodegradable poly(L‐lactide)/poly(ε‐caprolactone) and poly(L‐lactide)/poly(butylene succinate‐co‐L‐lactate) polymeric blends

Two series of biodegradable polymer blends were prepared from combinations of poly(L ‐lactide) (PLLA) with poly(?‐caprolactone) (PCL) and poly(butylene succinate‐co‐L ‐lactate) (PBSL) in proportions of 100/0, 90/10, 80/20, and 70/30 (based on the weight percentage). Their mechanical properties were investigated and related to their morphologies. The thermal properties, Fourier transform infrared spectroscopy, and melt flow index analysis of the binary blends and virgin polymers were then evaluated. The addition of PCL and PBSL to PLLA reduced the tensile strength and Young's modulus, whereas the elongation at break and melt flow index increased. The stress–strain curve showed that the blending of PLLA with ductile PCL and PBSL improved the toughness and increased the thermal stability of the blended polymers. A morphological analysis of the PLLA and the PLLA blends revealed that all the PLLA/PCL and PLLA/PBSL blends were immiscible with the PCL and PBSL phases finely dispersed in the PLLA‐rich phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compatibility of polysaccharide/maleic copolymer blends. IV. Thermal behavior of hydroxypropyl cellulose‐containing blends

The compatibility of the hydroxypropyl cellulose (HPC) with maleic acid–vinyl acetate copolymer in the solid state was studied by thermogravimetry, thermo‐optical analysis, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and optical microscopy. It was established that physical interactions are prevalent in blends with a high content of HPC, whereas chemical interactions predominate in blends with a medium and low content of HPC. By increasing the temperature, the thermochemical reactions are favored. Thermal properties are dependent on the mixing ratio of the components. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2585–2597, 2003     

Design and development of low‐cost optical‐fiber sensors for temperature metrology: Process monitoring of an epoxy resin system

This article reports the design and deployment of two optical‐fiber temperature sensors based on the fiber Fabry–Perot etalon. The first involved the use of an extrinsic fiber Fabry–Perot sensor, but in this instance, the coefficient of thermal expansion of the reflector and/or capillary was chosen to offer a mismatch. Hence, the cavity length could increase or decrease according to the coefficient of thermal expansion of the fiber and/or capillary. For comparison, single‐mode and multimode optical‐fiber Bragg gratings were also used as temperature sensors. The Fabry–Perot sensors operated from ?50 to 410°C. The accuracy of the measurements was up to ±0.5°C with a low‐cost charged‐coupling‐device spectrometer. The sensors also worked effectively in a microwave oven and in a composite panel in an autoclave. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 83–95, 2004     

Effect of side‐chain length of succinic anhydride on coefficient of thermal expansion behavior of epoxy resins

The effect of an alkenyl side‐chain of succinic anhydride (SA) on the thermal behavior and the coefficient of thermal expansion (CTE) of diglycidylether of bisphenol A (DGEBA) epoxy resins was studied. The number of carbons in the side‐chain of SA was varied from 6 to 14 and N,N‐Dimethylbenzylamine was used as an accelerator. As a result, the reactivity of SA with epoxide groups was decreased on increasing the length of the alkenyl side‐chain of SA. The thermal stabilities of cured DGEBA/SA samples were approximately constant with varying alkenyl side‐chain of SA. Also, the CTE of the systems was increased as the length of the alkenyl side‐chain of SA increased. This could be attributed to the increased motion of the chain segments in the epoxy network structure induced by the longer alkenyl side‐chain of SA. The effect of amount anhydride, thermoplastics, and fillers on the CTE of the epoxy resins was also discussed. Copyright © 2006 Society of Chemical Industry     

On the compatibility of polysaccharide/maleic copolymer blends. II. Thermal behavior of pullulan‐containing blends

The compatibility of pullulan with maleic acid/vinyl acetate copolymers in the solid state in the form of thin films was studied with thermogravimetry, differential scanning calorimetry, infrared spectroscopy, and optical microscopy. With respect to morphology, blends with a content of pullulan greater than 85 wt % exhibited an even distribution of finely dispersed particles. The thermal properties were dependent on the mixing ratio, and the interactions between components were quite pronounced in the pullulan‐rich blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1782–1791, 2002     

Low‐temperature synthesis of nano‐to‐submicron size organo‐zinc oxide and its effect on properties of polybutadiene rubber

Nano‐to‐submicron sized particles of zinc oxide (ZnO) were synthesized by low temperature hydrolysis method. Organo‐ZnO was also synthesized by the aforementioned method in presence of polyethylene glycol (PEG‐2000). The synthesized ZnO particles were characterized by infra‐red spectroscopy, X‐ray diffraction, BET surface area, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). FTIR showed that PEG was present on the ZnO surface. Organo‐ZnO exhibited floral‐shape morphology consisting of concentric nanorods. The average diameter of the nanorods was ～ 250 nm as evident from SEM. TEM showed that the nanorods were made of ～ 50 nm sized small particles. UV‐absorbance property of ZnO was unaltered even after organic coating. Curing, physico‐mechanical and thermal properties of polybutadiene rubber compounded with organo‐ZnO were compared with those of standard commercial rubber grade ZnO and nano‐ZnO prepared by high and low temperature methods. The cure‐characteristics were studied with the help of moving die rheometer as well as differential scanning calorimetry (DSC). Crosslink‐density measurement along the DSC vulcanization exotherm showed better cure efficiency of organo‐ZnO. Organo‐ZnO containing compound exhibited better mechanical and thermal properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Compatibility study in natural rubber and maize starch blends

Blends containing various ratios of natural rubber (NR) and maize starch (MS) were prepared on a two roll mill. The effect of starch contents on physico-mechanical properties and curing characteristics of the prepared blend vulcanizates was investigated. The data indicate poor mechanical properties, delayed cure rate index, and decreased maximum torque with increasing starch content in the blend formulation. This indicates that the interfacial interaction between the blend components was poor. Various contents of the compatibilizers, maleic acid anhydride (MAH) and glycidyl methacrylate (GMA), were mixed with the blend NR/MS (90/10). The effect of the compatibilizer contents on the physico-mechanical properties and curing characteristics of the binary blend was investigated. Compatibilized blends with GMA (1 phr) showed an improvement in the physico-mechanical properties in comparison with uncompatibilized blend samples. Blends with MAH exhibited higher modulus and hardness values with respect to GMA blends. The efficiency of the compatibilizers was also evaluated by studies of phase morphology (scanning electron microscope), Fourier transform infrared spectroscopy, and thermal stability (thermogravimetric analysis). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Artificial weathering effect on the structure and properties of polypropylene/polyamide‐6 blends compatibilized with PP‐g‐MA

The degradation of uncompatibilized and compatibilized PP/PA‐6 (70/30 wt %) with PP‐g‐MA under accelerated UV light was investigated using Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, melt flow index (MFI) tester, tensile test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR analysis of the structure of the compatibilized and uncompatibilized blends after exposure to UV light showed the formation of photoproducts corresponding to both components. The MFI and mechanical results obtained revealed that photooxidation started primarily in PA‐6 rather than PP. In addition, the uncompatibilized blends exhibited a higher degradation rate compared to neat polymers for long exposure time, and the addition of PP‐g‐MA increased slightly their ageing rate in accordance with TGA data. Further, DSC analysis showed an increase in the crystallinity index and a decrease in the melting temperature of PP and PA‐6 after UV exposure either as neat polymers or as blend components. SEM micrographs of the cryo‐fractured surfaces of the samples illustrated the formation of cracks and fractures after UV irradiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41722.     

Polymer blends of epoxy resin and epoxidized natural rubber

The aim of this research was to investigate the behaviors of epoxy resin blended with epoxidized natural rubber (ENR). ENRs were prepared via in situ epoxidation method so that the obtained ENRs contained epoxide groups 25, 40, 50, 60, 70, and 80 mol %. The amounts of ENRs in the blends were 2, 5, 7, and 10 parts per hundred of epoxy resin (phr). From the results, it was found that the impact strength of epoxy resin can be improved by blending with ENRs. Tensile strength and Young's modulus were found to be decreased with an increasing amount of epoxide groups in ENR and also with an increasing amount of ENR in the blends. Meanwhile, percent elongation at break slightly increased when ENR content was not over 5 phr. In addition, flexural strength and flexural modulus of the blends were mostly lower than the epoxy resin. Scanning electron microscope micrograph of fracture surface suggested that the toughening of epoxy resin was induced by the presence of ENR globular nodules attached to the epoxy matrix. TGA and DSC analysis revealed that thermal decomposition temperature and glass transition temperature of the samples were slightly different. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 452–459, 2006     

Fracture toughness of bisphenol A‐type epoxy resin

The relationship between the postcuring conditions and the fracture toughness of a bisphenol A‐type epoxy resin cured with acid anhydride was investigated. The glass transition temperature and fragility parameter, derived from the thermo‐viscoelasticity, were used to characterize the epoxy resin postcured under various conditions. Relationship between these two parameters and the fracture toughness was then investigated, based on the fractography results of a microscopic roughness examination of a fractured surface. The values of the glass transition temperature and fragility greatly depended on the postcuring conditions. The glass transition temperature was approximately 400 K when the crosslinking reaction was saturated. The fragility was independent of the saturation of the reaction and varied between 50 and 180. The results of the fracture test and fractography examination showed that there was no direct correlation between the glass transition temperature, the fracture toughness, and the roughness. On the other hand, there was a correlation between the fragility, fracture toughness, and roughness when the glass transition temperature saturated (at 400 K). As the fragility decreased from 180 to 50, the fracture toughness increased from 0.6 to 1.1 MPa · m^1/2 at the same glass transition temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 10: 2266–2271, 2002     

Fracture toughness of silica particulate‐filled epoxy composite

The relationship between the postcuring conditions and fracture toughness on three silica particulate‐filled epoxy composites was investigated. The glass transition temperature, T_g, and the fragility parameter, m, derived from the thermo‐viscoelasticity, were used to characterize the composites, which were postcured under various conditions. The glass transition temperature and fragility both depended on both of the curing conditions and the volume fraction of silica particles. The glass transition temperature increased with the postcuring time and temperature, while the fragility generally decreased as the volume fraction increased. There was no direct correlation between the glass transition temperature and fragility. The fracture toughness depended on both the glass transition temperature and fragility. The composites with a high glass transition temperature and low fragility had high fracture toughness. These results indicate that the glass transition temperature and fragility are useful parameters for estimating the fracture toughness of the silica particulate‐filled epoxy composites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2261–2265, 2002     

Mechanical and thermal properties of novel rubber‐toughened epoxy blend prepared by in situ pre‐crosslinking

A novel method is used for preparing liquid rubber‐toughened epoxy blend, in which an initiator was added to the liquid rubber–epoxy mixture to initiate crosslinking reaction of liquid rubber, and then curing agent was added to form the thermoset. Two epoxy blends with carboxyl‐terminated butadiene‐acrylonitrile copolymers were prepared using traditional and novel methods respectively. Results indicated that the novel rubber‐toughened epoxy blend exhibited much better mechanical properties than its traditional counterpart. The morphologies of the blends were explored by transmission electron microscopy (TEM), it was revealed that the use of the novel method formed a local interpenetrating network structure in the blend, which substantially improved the interfacial adhesion. The impact fracture surfaces of the two blends were observed by scanning electron microscopy (SEM) to explore the toughening mechanism, it was found that crack pinning was the major toughening mechanism for the novel rubber‐toughened epoxy blend. Dynamic mechanical analysis (DMA) was applied to determine the T_g values of the blends, which were found to be close. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41110.     

Thermal,thermo‐mechanical,and dynamic mechanical properties of polypropylene/cycloolefin copolymer blends

Interaction of the components and physical properties of the polypropylene (PP)/cycloolefin copolymer (COC) blends were studied by means of differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), Vicat softening temperature (VST), and measurements of the coefficient of linear thermal expansion (CLTE) and of the density. The attention was focused on the blends with 90–60% of PP by wt, where the COC minority component was present in the form of short fibers. DSC, DMTA, and density measurements concurrently prove the immiscibility of PP and COC. DSC measurements reveal that crystallinity and melting temperature of the PP component slightly decrease with the fraction of COC in blends, in the range of 56–47% and 164–161°C, respectively. Storage modulus and loss modulus of the blends are in a good accord with the model predictions based on (i) the equivalent box model (EBM) and on (ii) modified equations of the percolation theory. The dependence of the VST on the blend composition is in a good correlation with the previous morphological analysis. Measurements of the coefficient of thermal expansion provide useful data as the functions of temperature and blend composition. Density of the blends was found to obey the volume additivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Thermal and mechanical properties of linear low‐density polyethylene/low‐density polyethylene/wax ternary blends

The thermal and mechanical properties of uncrosslinked three‐component blends of linear low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and a hard, paraffinic Fischer–Tropsch wax were investigated. A decrease in the total crystallinity with an increase in both LDPE and wax contents was observed. It was also observed that experimental enthalpy values of LLDPE in the blends were generally higher than the theoretically expected values, whereas in the case of LDPE the theoretically expected values were higher than the experimental values. In the presence of higher wax content there was a good correlation between experimental and theoretically expected enthalpy values. The DSC results showed changes in peak temperature of melting, as well as peak width, with changing blend composition. Most of these changes are explained in terms of the preferred cocrystallization of wax with LLDPE. Young's modulus, yield stress, and stress at break decreased with increasing LDPE content, whereas elongation at yield increased. This is in line with the decreasing crystallinity and increasing amorphous content expected with increasing LDPE content. Deviations from this behavior for samples containing 10% wax and relatively low LDPE contents are explained in terms of lower tie chain fractions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1748–1755, 2005