Phthalonitrile‐epoxy blends: Cure behavior and copolymer properties

Binary blends composed of 4,4′‐bis(3,4‐dicyanophenoxy)biphenyl (biphenyl PN) and diglycidyl ether of bisphenol A (epoxy resin) and oligomeric n = 4 phthalonitrile (n = 4 PN) and epoxy resin were prepared. The cure behavior of the blends was studied under dynamic and isothermal curing conditions using differential scanning calorimetry, simultaneous thermogravimetric/differential thermal analysis, infrared spectroscopy, and rheological analysis. The studies revealed that phthalonitrile‐epoxy blends exhibited good processability and that they copolymerized with or without the addition of curing additive. In the absence of curing additive, the blends required higher temperatures and longer cure times. The thermal and dynamic viscoelastic properties of amine‐cured phthalonitrile‐epoxy copolymers were examined and compared with those of the neat epoxy resin. The properties of the epoxy resin improved with increasing biphenyl PN content and with n = 4 PN addition. Specifically, the copolymers exhibited higher glass transition temperatures, increased thermal and thermo‐oxidative stabililty, and enhanced dynamic mechanical properties relative to the commercially available epoxy resin. The results showed that the phthalonitrile‐epoxy blends and copolymers have an attractive combination of processability and high temperature properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dielectric behavior and properties of a cyanate ester containing dicyclopentadiene. I

2,6‐Dimethyl phenol dicyclopentadiene dicyanate ester (DCPDCY) was synthesized through the reaction of 2,6‐dimethyl phenol dicyclopentadiene novolac and cyanogen bromide. The proposed structure was confirmed by Fourier transform infrared, mass spectrometry, NMR spectrometry, and elemental analysis. DCPDCY was then cured by itself or cured with bisphenol A dicyanate ester (BADCY) to form triazine structures. The thermal properties of the cured DCPDCY resins were studied with differential scanning calorimetry, dynamic mechanical analysis (DMA), dielectric analysis, and thermogravimetric analysis; these data were compared with those of BADCY. The cured DCPDCY resins exhibited a lower dielectric constant (2.58 at 1 MHz), a lower dissipation factor (20.2 mU at 1 MHz), less thermal stability (the 5% degradation temperature and char yield were 430°C and 32.1%, respectively), a lower glass‐transition temperature (266°C by thermomechanical analysis and 271°C by DMA), a lower coefficient of thermal expansion (22.5 ppm before the glass‐transition temperature and 124.9 ppm after the glass‐transition temperature), and less moisture absorption (0.88% at 48 h) than BADCY, but they showed higher moduli (6.28 GPa at 150°C and 5.35 GPa at 150°C) than the bisphenol A system. The properties of the cured cocyanate esters (DCPDCY and BADCY) lay between those of cured BADCY and DCPDCY, except for the moduli. The moduli of some cocyanate esters were even higher than those of cured BADCY and DCPDCY. A positive deviation from the Fox equation was observed for cocyanate esters. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2079–2089, 2005     

Dielectric and thermal properties of polymer network based on bismaleimide resin and cyanate ester containing dicyclopentadiene or dipentene. III

A series of bismaleimide‐triazine (BT) resins were prepared from commercial bismaleimide (DDMBMI) and 2,6‐dimethylphenol‐dicyclopentadiene dicyanate ester (DCPDCY) or 2,6‐dimethylphenol‐dipentene dicyanate ester (DPCY). The thermal properties of cured BT resins containing DCPD or DP were studied using a dielectric analyzer (DEA), dynamic mechanical analyzer (DMA), and thermal gravimetric analyzer (TGA). These data were compared with that of DDMBMI cured with bisphenol A dicyanate ester (BADCY). The cured DDMBMI/DCPDCY or DDMBMI/DPCY exhibits a lower dielectric constant, dissipation factor, and moisture absorption than those of DDMBMI/BADCY. The effects of blend composition on the glass transition temperatures and thermal stability are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1942–1951, 2007     

Curing and thermal behavior of diglycidyl ether of bisphenol A in the presence of a mixture of amines

The curing behavior of diglycidyl ether of bisphenol A (DGEBA) was investigated by differential scanning calorimetry with mixtures of silicon‐containing amide–amines and diaminodiphenyl sulfone (DDS). Silicon‐containing amide–amines were prepared by the reaction of 2.5 mol of 4,4′‐diaminodiphenyl ether (E), 4,4′‐diaminodiphenyl methane (M), 3,3′‐diaminodiphenyl sulfone (mS), 4,4′‐diaminodiphenyl sulfone (pS), bis(3‐aminophenyl) methyl phosphine oxide (B), or tris(3‐aminophenyl) phosphine oxide (T) with 1 mol of bis(4‐chlorobenzoyl) dimethyl silane. Mixtures of the amide–amines and DDS at ratios of 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0 were used to investigate the curing behavior of DGEBA. A single exotherm was observed on curing with a mixture of amide–amine and DDS. This clearly shows that the mixture participated in the cocuring reaction. The peak exotherm temperature depended on the structure and the molar ratio of amide–amines. With all of the amide–amines and DDS, a significant decrease in the kick‐off temperature of the curing exotherm was observed on the incorporation of a 0.25 molar fraction of amide–amines. Thus, with the mixture, the curing temperatures were reduced and were lowest for ether‐containing amide‐amines and highest for methylene‐containing amide–amines. The char yield was almost similar in the samples cured with amide–amines (E, pS, or mS) or DDS. The char yield was higher than for either of the constituents when a mixture was used. A synergistic behavior was observed when a mixture of E, M, mS, or pS and DDS was used, whereas mixture of B or T and DDS showed antigonism in the char yield. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1739–1747, 2003     

Curing characteristics,morphology, thermal stability,mechanical properties,and irradiation resistance of methylethylsilicone/methylphenylsilicone rubber blends

Methylethylsilicone rubber (MESR)/methylphenylsilicone rubber (MPSR) blends were cured with 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy)hexane. The curing characteristics, morphology, thermal behaviors, mechanical properties at different temperatures, radiation resistance, and thermal aging resistance of the MESR/MPSR blends were investigated. The results show that a high MPSR content could decrease the optimum curing time and improve the scorch safety. Dynamic mechanical analysis revealed that the glass‐transition temperature of the blends increased slightly with the addition of MPSR. Scanning electron microscopy showed that MESR and MPSR had good compatibility in the blends. Thermogravimetric analysis indicated that the thermal stability of the blends increased with increasing quantity of MPSR. The blends had excellent mechanical properties at low temperatures. However, these properties were significantly reduced when the temperature was increased. Moreover, changes in the mechanical properties decreased with increasing MPSR content at high temperatures, especially at temperatures higher than 100°C. In addition, the radiation resistance and thermal aging resistance of the blends increased with increasing MPSR content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40529.     

Studies on mechanical and thermal properties of ternary blends of polyethylenes. I

Six film samples of varying compositions of linear low‐density polyethylene (LLDPE), 10–35 wt %, and high‐density polyethylene (HDPE), 40–65 wt %, having a fixed percentage of low‐density polyethylene (LDPE) at 25 wt % were extruded by melt blending in a single‐screw extruder (L/D ratio = 20 : 1) of uniform thickness of 2 mil. The tensile strength, elongation at break, and impact strength were found to increase up to 60 wt % HDPE addition, starting from 40 wt % HDPE, in the blends and then decreased. The blend sample B‐500 was found to be more thermally stable than its counterparts. The appearance of a single peak beyond 45 wt % HDPE content in the blend in dynamic DSC scans showed the formation of miscible blend systems and this was further confirmed by scanning electron microscopic analysis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1691–1698, 2005     

Understanding of intermolecular interaction in PVDF/PTW blends: Crystallization behavior,thermal, and dynamic mechanical properties

Poly(vinylidene fluoride) (PVDF)/ poly(ethylene–butylacrylate–glycidyl methacrylate) (PTW) blends were directly prepared by melt blending and the interaction and properties of PVDF/PTW blends were explored systematically. The crystallization behavior, thermal stability, dynamic mechanical property, and morphological features of PVDF/PTW blends with different ratios have been studied by XRD, attenuated total reflection Fourier transform infrared spectroscopy, differential scanning calorimeter analysis (DSC), thermal gravimetric analysis (TGA), dynamic mechanical analysis, and polarized optical microscopy (POM). The results showed that the crystalline structure of neat PVDF was dominantly α‐phase crystalline and the incorporation of PTW had no effect on the crystalline structure of PVDF in the PVDF/PTW blends. And T_g of PVDF in PVDF/PTW blends shifted to higher temperature compared with that of neat PVDF, indicating the weak interaction between PVDF and PTW, which was corresponding to DSC and TGA results. An increase in the coarseness and ring‐band spacing observed from POM further substantiated the weak interaction between PVDF and PTW. This work provided a way for preparing improved properties of PVDF/PTW blends for the coating material. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43908.     

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     

Analysis of mechanical,thermal, and morphological behavior of polycaprolactone/wood flour blends

In the present study, the properties of polycaprolactone (PCL) and wood flour (WF) blends were examined by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), Instron mechanical tester, and scanning electron microscopy (SEM). As for results, the mechanical properties of PCL were lowered obviously, due to the poor compatibility between the two phases, when it was blended with wood flours. A fine dispersion and homogeneity of wood flour in the polymer matrix could be obtained when the acrylic acid grafted PCL (PCL‐g‐AA) was used to replace PCL for manufacture of blends. This better dispersion is due to the formation of branched and crosslinked macromolecules since the PCL‐g‐AA copolymer had carboxyl groups to react with the hydroxyls. This is reflected in the mechanical and thermal properties of the blends. In comparison with pure PCL/WF blend, the increase in tensile strength at break was remarkable for PCL‐g‐AA/WF blend. The PCL‐g‐AA/WF blends are more easily processed than the PCL/WF ones since the former had lower melt viscosity than the latter. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1000–1006, 2004     

Study on mechanical,thermal and shape memory properties of polycarbonate/thermoplastic polyurethane blends

The objective of the study is preparation of shape memory blend of polycarbonate (PC) and thermoplastic polyurethane (TPU). Polycarbonate is blended with three types of TPUs and subsequently mechanical, thermal, morphological, and shape memory properties of the PC/TPU blends are studied. When TPU content in the blend is higher than 40% (by weight), the glass transition temperature related to PC is not shown in the differential scanning calorimetry thermogram, indicating loss of PC properties. The 60/40 optimized blend of PC/TPUs exhibits maximum increment of about 1100% in elongation and 43% decrement in tensile strength. The shape recovery of the optimized blend obtained by addition of 40% (by weight) of TPUs in PC polymer is found to be 65% and shape fixity is 97%. These results suggest that the blend of PC/TPU may be utilized for various applications where shape memory property is required including strategic applications.     

Mechanical and thermal properties of bisphenol A-based cyanate ester and diallyl phthalate blends

Cyanate ester resins are a high performance class of compounds. They have excellent mechanical properties, dielectric properties and thermal properties; however, their major drawback is their brittleness. An attempt was made to improve the impact strength of the cyanate ester resin. In the present study a commonly used cyanate resin, bisphenol A dicyanate (BADCy), was modified by the addition of diallyl phthalate (DAP) and was cured with benzoyl peroxide. The properties of the blends such as thermal and mechanical properties were investigated in detail by scanning electron microscope, dynamic mechanical analysis, thermogravimetric analysis, and mechanical measurement. The results indicate that the addition of the appropriate amount of DAP can effectively improve the impact toughness and the flexural strength while sacrificing the thermal properties of the blends. The maximum impact strength and flexural strength were observed on addition of 15 phr DAP content. However, the thermal stability of the blends was found to be lower than that of the unmodified BADCy resin.     

The impact of polymer matrix blends on thermal and mechanical properties of boron nitride composites

To improve mechanical and thermal properties of a hexagonal boron nitride platelet filled polymer composites, maleic anhydride was studied as a coupling agent and compatibilizer. Injection molded blends of acrylonitrile butadiene styrene (ABS), high-density polyethylene (HDPE), and maleic anhydride with boron nitride filler were tested for thermal conductivity and impact strength to determine whether adding maleic anhydride improved interfacial interactions between matrix and filler and between the polymers. Adding both HDPE and maleic anhydride to ABS as the matrix of the composite resulted in a 40% improvement in impact strength without a decrease in thermal conductivity when compared to an ABS matrix. The best combination of thermal conductivity and impact strength was using pure HDPE as the matrix material. The effective medium theory model is used to help explain how strong filler alignment helps achieve high thermal conductivity, greater than 5 W/m K for 60 wt % boron nitride. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48661.     

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     

Mechanical properties,oil resistance,and thermal aging properties in chlorinated polyethylene/natural rubber blends

The use of natural rubber (NR) for partly substituting elastomeric chlorinated polyethylene (CPE) was determined. Mechanical and thermal aging properties as well as oil resistance of the blends were also investigated. The amount of NR in blends significantly affected the properties of the blends. The blends with NR content up to 50 wt % possessed similar tensile strength to that of pure CPE even after oil immersion or thermal aging. Modulus and hardness of the blends appeared to decrease progressively with increasing NR content. These properties also decreased in blends after thermal aging. After oil immersion, hardness decreased significantly for the blends with high NR content, whereas no change in modulus was observed. The dynamic mechanical properties were determined by dynamic mechanical thermal analysis. NR and CPE showed damping peaks at about ?40 and 4 °c, respectively; these values correlate with the glass‐transition temperatures (T_g) of NR and CPE, respectively. The shift in the T_g values was observed after blending, suggesting an interfacial interaction between the two phases probably caused by the co‐vulcanization in CPE/NR blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 22–28, 2002; DOI 10.1002/app.10171     

A study on mechanical and thermal properties of silicone rubber/EPDM damping materials

Silicone rubber (SR) and ethylene‐propylene‐diene monomer (EPDM) blends were prepared for damping application. The mechanical and thermal properties of the blends are studied. With the increasing content of EPDM, the tensile strength is decreased but elongation at break is increased. By blending with EPDM, tan δ (at 35 to 200°C) of SR is enhanced. However, thermogravimetric analysis results showed the decrease in thermal stability. Scanning electron microscopy study showed the good filler dispersion of the blends with some large silica particles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High‐performance polymeric materials with greatly improved mechanical and thermal properties from cyanate ester/benzoxazine resin reinforced by silane‐treated basalt fibers

This present article investigates the effect of silane‐treated basalt fibers (TBFs) on the morphological, mechanical and thermal properties of cyanate ester/benzoxazine (CE/BOZ) resin composites. The characterization was made using a scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), flexural test, impact strength (IS) test, microhardness test, dynamic scanning calorimetry, and thermogravimetric analysis. The mechanical test results inferred the distinctive improvements in the values of the flexural strength and modulus, IS, and microhardness of the CE/BOZ composites. The thermal stabilities in terms of the T_g, T_5%, T_10%, and T_HRI were appreciably improved and were higher than those of the pure CE/BOZ resin. Data from the SEM and FTIR tests ascertained the good dispersion and adhesion between the TBFs and the resin matrix, which might be behind the significant enhancement in the ultimate performances of the composites, with respect to the distinguished properties of BFs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46283.     

Study on effects of short glass fiber reinforcement on the mechanical and thermal properties of PC/ABS composites

This article mainly investigated the length distributions of the alkali‐free short glass fibers in specimens and their effect on the mechanical and thermal properties of the composites. The results show that the initial length, addition level and feed way of the fibers have obvious effects on the length distributions of fibers in specimens, and thereby the mechanical and thermal properties of the composites. The main‐direction feed way has an intense shear action on the fibers in specimens. With the increase of the fiber content, the reinforcing effect of fibers on the tensile strength, flexural strength and flexural modulus of the composites is increased, while the impact strength is decreased first and then tends to be stable, and the strength factor (F) of the tensile strength to weld line is significantly reduced. The longer the fiber lengths in specimens are, the more obvious the reinforcing and toughening effects are. To some extent, with the increase of the fiber content, the storage modulus (E′) and loss modulus (E′′) of the specimens are increased, but the loss factor (Tan δ) is reduced. The effect of the fiber initial lengths on the heat‐degradation of composites is smaller than that of the fiber content. Meanwhile, adding fibers can improve the thermal stability of the composites, and this law is also confirmed by the heat deflection temperature (HDT) test. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40697.     

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.     

Frontal polymerization of a cyanate ester

Thermal frontal polymerization is an exothermic process that uses a propagating wave to polymerize monomers via an external heat source, such as a soldering iron, to initiate front propagation. Herein, for the first time, the curing of a cyanate ester via thermal frontal polymerization is described with two different external heat sources. However, issues of bubbling due to vaporization of the amine catalyst generally resulted in incomplete frontal polymerization when a soldering iron was used as the external heat source. To counter this issue, dual‐strip polymerization systems were used, wherein the heat from the exothermic polymerization of a free‐radical system was used to initiate the frontal polymerization of a cyanate ester system with an amine catalyst. As a result, complete frontal polymerization occurred. Additionally, the effect of the width of the acrylate strip and its impact on the front temperature, initial velocity, and steady‐state velocity of the adjacent cyanate ester system were studied. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and mechanical evaluation of cyanate ester resin catalyzed by nonylphenol and stannous octoate

Nonylphenol (NP), stannous octoate [Sn(Otc)₂], and a mixture of NP and Sn(Otc)₂ were employed for catalyzing cyanate ester resin. The curing reaction was studied by differential scanning calorimetry. A water‐absorption test at 85 °C was utilized to study the resistance to warm and humid conditions. The thermal properties were evaluated through measuring thermal weight loss and the glass‐transition temperature (T_g), and the mechanical properties were evaluated through three‐point bending tests and tensile tests. The results show that the mixture of NP and Sn(Otc)₂ exhibits the best catalytic efficiency by decreasing the exothermic peak temperature by almost 148 °C. The mixture of NP and Sn(Otc)₂ has unfavorable effects on the thermal stability. Nevertheless, all catalyst systems have good water‐absorption resistance. The mechanical investigation confirms that the tensile properties show a little reduction that is due to the plasticization of the catalyst, while the excellent flexural properties are maintained. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43959.