Influence of crosslinking methods toward poly(vinyl alcohol) properties: Microwave irradiation and conventional heating

In this study, crosslinking of poly(vinyl alcohol) (PVA) with tartaric acid, as crosslinker, is performed using microwave irradiation. A comparison between the properties of PVA crosslinked using microwave irradiation and conventional heating methods is also discussed. While the water absorption, tensile and thermal properties of PVA crosslinked by either of the methods are comparable, microwave irradiation took only one‐eighth (14 min) of the time compared to conventional heating. In comparison with PVA (42 MPa), the strength of PVA crosslinked with 35% TA increased to 145 and 153 MPa for conventional heating and microwave irradiation, respectively. Water absorption of crosslinked PVA film is successively reduced to less than 30% in comparison with PVA (～200%). Moreover, the crosslinked films are stable at higher temperatures in comparison with PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46125.     

Preparation and properties of glass cloth‐reinforced polyimide composites with improved impact toughness for microelectronics packaging substrates

A series of glass cloth‐reinforced thermosetting polyimide composites (EG/HTPI) were prepared from E‐glass cloth (EG) and polyimide matrix resins. The polyimide resins were derived from 1,4‐bis(4‐amino‐2‐ trifluoromethyl‐phenoxy)benzene, p‐phenylenediamine, diethyl ester of 3,3′,4,4′‐benzophenonetetracarboxylic acid, and monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid. Based on the rheological properties of the B‐staged polyimide resins, the optimized molding cycles were designed to fabricate the EG/HTPI laminates and the copper‐clad laminates (Cu/EG/HTPI). Experimental results indicated that the EG/HTPI composites exhibited high thermal stability and outstanding mechanical properties. They had flexural strength of >534 MPa, flexural modulus of >20.0 GPa, and impact toughness of >46.9 kJ/m². The EG/HTPI composites also showed good electrical and dielectric properties. Moreover, the EG/HTPI laminates exhibited peel strength of ～ 1.2 N/mm and great isothermal stability at 288°C for 60 min, showing good potential for application in high density packaging substrates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Microwave properties of carbon black–epoxy resin composites and their simulation by means of mixture laws

This article reports on a study of the dielectric properties of carbon black dispersions in an insulating epoxy matrix at microwave frequencies. Measurements showed that the complex permittivity of the composites depends strongly on the nature and concentrations of the conducting medium. The experimental values of the complex permittivity were compared to those obtained by using different mixing laws. We show that effective medium theories correctly account for the experimental results at low conducting particle concentrations. At concentrations higher than a few percent, these laws fail to interpret experimental results and all tentative results must take into account parameters such as the particle size, their distribution, and the existence of agglomerates. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 969–973, 1999     

Effect of coprecipitated barium ferrite on the cure characteristics and dynamic properties of natural rubber–ferrite composites around percolation

The influence of coprecipitated hexagonal barium ferrite BaFe₁₂O₁₉ phase on the cure characteristics and dynamic properties of natural rubber–ferrite composites has been studied as a function of ferrite loading up to 220 phr (part per hundred part of rubber). Unusual characteristics of coprecipitated ferrite particles were discovered by scanning electron microscope. The results show that scorch time t₁₀ and cure time t₉₀ decrease dramatically with increasing ferrite content up to critical ferrite loading. After 160 phr, t₉₀ increases sharply with increasing ferrite content, in contrast to saturation of t₁₀. Minimum torque recorded normal behavior at low ferrite loading, whereas it decreases with increasing ferrite content at high ferrite loading because of dilution effects. The storage modulus E′ and loss modulus E″ decrease with increasing temperature. The loss tangents (tanδ) of the composites are greater than those of the pure rubber. Linear viscoelastic behavior was observed as a result of the homogeneity and compatibility of the composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of starch-graft-poly(glycidyl methacrylate)–PHBV composites

The use of graft copolymers of starch and glycidyl methacrylate (starch-g-PGMA) to improve the mechanical properties of composites with poly(hydroxy butyrate-co-valerate) (PHBV) has been investigated. In general, the tensile and flexural strengths of the composites were greater with starch-g-PGMA compared to untreated starch and increased with increasing graft content. The modulus and elongation were not significantly changed by grafting. All samples gained weight after immersion in water for 28 days. Tensile strength and modulus decreased with water sorption, while the fracture toughness significantly increased with grafted starch. No differences were observed between properties of grafts prepared with ceric ammonium nitrate or ferrous sulfate–peroxide graft initiators. Scanning electron micrographs of cryogenic fracture surfaces showed improved adhesion between the starch-g-PGMA and the PHBV matrix. Although no spectroscopic evidence of reaction between PHBV and the starch-g-PGMA was found, the improvement in mechanical properties is consistent with enhanced interactions between the starch-g-PGMA and the PHBV matrix compared to ungrafted starch. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1121–1127, 1998     

Thermal and dynamic mechanical properties of organic–inorganic hybrid composites of itaconate‐containing poly(butylene succinate) and methacrylate‐substituted polysilsesquioxane

Itaconate‐unit‐containing poly(butylene succinate) (PBSI) was synthesized by the reaction of 1,4‐butanediol, succinic acid, and itaconic acid in a molar ratio of 2.0 : 1.0 : 1.0, and the obtained PBSI was reacted with methacryl‐group‐substituted polysilsesquioxane (ME‐PSQ) in the presence of benzoyl peroxide (BPO) at 130°C to produce PBSI/ME‐PSQ hybrid composites. The thermal and dynamic mechanical properties of the PBSI/ME‐PSQ hybrid composites were investigated in comparison with those of PBSI cured at 130°C in the presence of BPO. As a result, the hybrid composites showed a much higher thermal degradation temperature and storage modulus in the rubbery state than the cured PBSI (C‐PBSI). The thermal degradation temperature and storage modulus of the hybrid composites increased with increasing ME‐PSQ content. The glass‐transition temperature, measured by dynamic mechanical analysis of the hybrid composites, somewhat increased with increasing ME‐PSQ content. However, the glass‐transition temperatures of all the hybrid composites were lower than that of C‐PBSI. Although the IR absorption peak related to C?C groups was not detected for C‐PBSI, some olefinic absorption peaks remained for all the hybrid composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electromagnetic interference shielding effectiveness of graphite‐filled polypropylene and poly(ether imide) based composites

The electromagnetic interference shielding characteristics of polypropylene (PP) and poly(ether imide) (PEI) filled with synthetic graphite composites were studied. The thermal properties were characterized by differential scanning calorimetry and thermogravimetric analysis, whereas the morphologies of the composites were studied by scanning electron microscopy. The viscosity measurements were studied by advance rheometry. The measurements of shielding effectiveness (SE) were carried out in the frequency range 8–12 GHz (X‐band range). The return loss and loss due to absorption were also measured as a function of frequency in the X‐band range. It was observed that the SE of the composites was frequency dependent, and it increased with increasing frequency. The SE also increased with increasing filler loading. The PEI‐based composites showed a higher SE compared to that of the PP‐based composites. The correlation between SE and the conductivity of the various composites is also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adjustable amine–epoxy composition in a stratified thin film with a spin‐coating process: A useful tool for establishing relationships between the local glass‐transition temperature at the interface and the network structure

An easy method for preparing supported homogeneous epoxy–amine thin films on a silica surface consisting of two distinct layers was developed via spin coating from epoxy–amine solutions. Because of these two layers had the controlled properties of the upper layer, we showed that it was possible to precisely control the epoxy–amine stoichiometry in the sublayer through the initial epoxy–amine ratio, the spin‐cast process, and the overall film thickness. First, in the thin films, the primary amine–epoxy conversion was constant, whatever the thickness and initial epoxy–amine stoichiometry for a given curing schedule. As the primary amine conversion can be independently tuned in thin films, it thus provided a rather unique and easy method for better understanding the relationship between the network structure curing at the interface and the resulting properties, such as the glass‐transition temperature (T_g) and elastic modulus. Here, we also showed that we could access the local T_g; this implied a potential application of these experimental data in predictive composite material properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42078.     

Evolution of properties of an isocyanate/epoxy thermosetting system during cure: Continuous heating (CHT) and isothermal time—temperature—transformation (TTT) cure diagrams

The present article describes a methodology for examining the evolution of the properties vs. cure of a complex thermosetting isocyanate/epoxy reactive mixture which reacts through two consecutive but separable reaction regimes. The methodology is based on the use of the torsional braid analysis (TBA) technique and the continuous heating (CHT) and isothermal time—temperature—transformation (TTT) cure diagrams. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 15–25, 1997     

Thermal,mechanical, and surface characterization of starch–poly(vinyl alcohol) blends and borax‐crosslinked films

Starch–poly(vinyl alcohol) (PVA) blends with different compositions were prepared and crosslinked with borax by in situ and posttreatment methods. Various amounts of glycerol and poly(ethylene glycol) with a molecular weight of 400 were added to the formulations as plasticizers. The pure starch–PVA blends and the crosslinked blends were subjected to differential scanning calorimetry, thermogravimetry, and X‐ray photoelectron spectroscopic studies. Broido and Coats–Redfern equations were used to calculate the thermal decomposition kinetic parameters. The tensile strengths and elongation percentages of the films were also evaluated. The results suggested that the glass‐transition temperature (T_g) and the melting temperature strongly depended on the plasticizer concentration. The enthalpy relaxation phenomenon was dependent on the starch content in the pure blend. The crosslinked films showed higher stability and lower T_g's than pure PVA and starch–PVA blends, respectively. High‐resolution X‐ray photoelectron spectroscopy provided a method of differentiating the presence of various carbons associated with different environments in the films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1313–1322, 2005     

Effects of peroxide and phenolic cure systems on characteristics of the filled ethylene–propylene–diene monomer rubber (EPDM)

The effects of three curing systems, peroxide, peroxide–phenolic combination, and phenolic on selected properties of cured carbon black‐filled ethylene–propylene–diene monomer rubber (EPDM) were investigated. The cured rubbers immersed in hot amine solution to evaluate their suitability for seal and gasket industry at elevated temperature and amine environments. These tests were essential for evaluating the durability of the gasket in a gas refinery. The Fourier transform infrared spectroscopy spectrums revealed that the phenolic crosslink was constructed between rubber macromolecules during the curing process. The changing curing system from peroxide to peroxide–phenolic and phenolic increased the glass transition temperature of the filled cured rubbers between 3 and 5 °C. There was not any significant difference between thermogravimetric analysis thermographs of the selected cured rubbers with various cure systems and the residues ranged between 45% and 47%. Unlike of peroxide curing system, a dual phase was observed from scanning electron microscopy micrographs for peroxide–phenolic and phenolic cure systems. The phenolic cure system was not beneficial for rubber curing although, it reduced scorch time of the curing process. For the most studied mechanical properties, phenolic cure system deteriorated mechanical properties for both, aged and unaged cured rubbers. Increasing the amount of diene monomer in EPDM structure was beneficial for phenolic rubber cure system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46213.     

Time–temperature–transformation (TTT) cure diagrams: Relationship between Tg and the temperature and time of cure for a polyamic acid/polyimide system

Glass transition temperatures (T_g) were obtained vs. isothermal temperature (T_cure) and time of cure for a polyamic acid/polyimide system. A time–temperature–transformation (TTT) isothermal cure diagram was constructed to include the time to vitrification and iso-T_g curves. As for expoxies, the relationship between T_cure and the time to vitrification is S-shaped. Plots of T_g vs. T_cure show that solvent evaporation and chemical reaction are controlled by vitrification.     

Carbon/carbon composites derived from poly(ethylene oxide)‐modified novolac‐type phenolic resin: Microstructure and physical,and morphological properties

A poly(ethylene oxide) (PEO) novolac‐type phenolic resin blend was prepared by the physical blending method. The modified novolac‐type phenolic resin with various PEO contents was used as a matrix precursor to fabricate carbon/carbon composites. The effect of the PEO/phenolic resin mixing ratio on the change of the density and of the porosity was studied. The flexural strength and interlaminar shear strength of the PEO/phenolic resin blend‐derived carbon/carbon composites were also investigated. The results show that the density of the PEO/phenolic resin blend‐derived carbon/carbon composites decreases with the PEO content. The X‐ray diffraction and Raman spectra studies showed that the carbon fiber in the samples will affect the growth of the ordered carbon structure. From SEM morphological observation, it is shown that the fracture surface of specimens is smooth. Also, there is less fiber pull‐out and fiber breakage on the fracture surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1609–1619, 2002; DOI 10.1002/app.10407     

Novel heat resistant methyl‐tri(phenylethynyl)silane resin: Synthesis,characterization and thermal properties

Methyl‐tri(phenylethynyl)silane (MTPES) was successfully synthesized by the reaction of lithium phenylacetylide with methyltrichlorosilane. The structure was characterized by HRMS, FTIR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, and elementary analysis. Thermal cure process was monitored by DSC, DMA, and FTIR. MTPES was heated to free flowing liquid around 130°C and thermally polymerized at 327–377°C to form thermoset. Thermal and oxidative properties were evaluated by TGA analysis. Thermoset exhibits extremely high heat‐resistance and TGA curve in nitrogen shows the temperature of 5% weight loss (Td₅) of 695°C and total weight loss at 800°C of 7.1%. TGA shows a high Td₅ of 565°C even in air, although the total weight loss at 800°C was 56.1% of the initial weight, much higher than that in nitrogen. The high heat resistance of MTPES was ascribed to crosslinking reaction concerning ethynyl groups. Aging studies performed at elevated temperatures in air on a thermoset showed that MTPES is oxidatively stable to 300°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2488–2492, 2006     

Fabrication and properties of carbon nanotube/styrene–ethylene–butylene–styrene composites via a sequential process of (electrostatic adsorption aided dispersion)‐plus‐(melt mixing)

Carbon nanotube (CNT)/styrene–ethylene–butylene–styrene (SEBS) composites were prepared via a sequential process of (electrostatic adsorption assisted dispersion)‐plus‐(melt mixing). It was found that CNTs were uniformly embedded in SEBS matrix and a low percolation threshold was achieved at the CNT concentration of 0.186 vol %. According to thermal gravimetric analysis, the temperatures of 20% and 50% weight loss were improved from 316°C and 352°C of pure SEBS to 439°C and 463°C of the 3 wt % CNT/SEBS composites, respectively. Meanwhile, the tensile strength and elastic modulus were improved by about 75% and 181.2% from 24 and 1.6 MPa of pure SEBS to 42 and 4.5 MPa of the 3 wt % CNT/SEBS composite based on the tensile tests, respectively. Importantly, this simple and low‐cost method shows the potential for the preparation of CNT/polymer composite materials with enhanced electrical, mechanical properties, and thermal stability for industrial applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40227.     

Mechanical and dielectric properties of cured 1,2‐bis(vinylphenyl)ethane resin modified with poly(phenylene oxide)

1,2‐Bis(vinylphenyl)ethane (BVPE) could be cured without curing agents at relatively low temperatures (～ 180°) in a nitrogen atmosphere. Cured BVPE (CBVPE) resin showed exceptionally low dielectric constant (? = 2.50 at 10 GHz) and low dielectric loss tangent (tan δ = 0.0012 at 10 GHz), and had excellent thermal resistance. Its 5 wt % weight‐loss temperature was 425°C in a nitrogen atmosphere and glass transition temperature was over 400°C. Poly(phenylene oxide) (PPO) was used to improve the toughness of CBVPE resin. PPO was an effective modifier to toughen CBVPE resin: when using 30 wt % of the modifier, the tensile strength and elongation of the modified CBVPE resin were 75 MPa and 26%, respectively. The modified CBVPE resin also showed excellent dielectric properties (? = 2.45 at 10 GHz, tan δ = 0.0015 at 10 GHz). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1252–1258, 2004     

Study on the properties of crosslinking of poly(ethylene oxide) and hydroxyapatite–poly(ethylene oxide) composite

This study covers the crosslinking of poly(ethylene oxide) (PEO) and its composite with calcium hydroxyapatite (HA), their mechanical and swelling properties, and morphology. Sheets of the composites of PEO (two different grades with M_v: 5 × 10⁶ and 2 × 10⁵) and HA and neat PEO were prepared by compression molding. The prepared composite and PEO (0.1‐mm‐thick) sheets were crosslinked with exposure of UV‐irradiation in the presence of a photoinitiator, acetophenone (AP). This simple method for crosslinking, induced by UV‐irradiation in the presence of AP, yielded PEO with gel content up to 90%. Gel content, equilibrium swelling ratio, and mechanical and morphological properties of the low molecular weight polyethylene oxide (LMPEO)–HA crosslinked and uncrosslinked composites were evaluated. Although the inclusion of HA into LMPEO inhibits the extent of crosslinking, the LMPEO–HA composite with 20% HA by weight shows the highest gel content, with appreciable equilibrium swelling and mechanical strength. The growth of HA in simulated body fluid solutions on fractured surfaces of LMPEO and also LMPEO–HA was found to be very favorable within short times. The dimensional stability of these samples was found to be satisfactory after swelling and deposition experiments. The good compatibility between the filler hydroxyapatite and poly(ethylene oxide) makes this composite a useful tissue‐adhesive material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 488–496, 2003     

Reactive blends of epoxy resin (DGEBA) crosslinked by anionically polymerized polycaprolactam: Process of epoxy cure and kinetics of decomposition

The curing reactions, kinetics, morphology, and thermal stability of the reactive blends of diglycidyl ether of bisphenol‐A (DGEBA) and polycaprolactam were studied by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis. DSC studies showed that the heat of reaction (ΔH) increased when the DGEBA content was increased from 50 to 80 wt % and increased drastically above 70 wt % DGEBA content because of an increase in the extent of crosslinking. The activation energy and pre‐exponential factor of cure reactions increased drastically with an increase in the DGEBA content above 70 wt % because of a drastic increase in crosslink density. The extent of curing reaction of polycaprolactam with DGEBA is dependent on the blend composition. The nucleophilic attack on oxirane ring by amide nitrogen of polycaprolactam is a dominant curing reaction in low DGEBA compositions, and another type of curing reaction with relatively large activation energy and pre‐exponential factor also occurred, which becomes dominant when the DGEBA content reaches above 70 wt %. FTIR studies also revealed that two types of reactions do exist during the curing of polycaprolactam with DGEBA. It was observed during SEM studies that the reactive blends show multiphase system and on increasing the DGEBA content from 50 to 80 wt %, the mixing of the two phases increased. The reactive blend Ep₈₀Ca₂₀ with 80 wt % DGEBA content exhibits a single‐phase system because of better mixing of the two phases. The results of thermogravimetric analysis also indicate that the initial degradation temperature (T_i), activation energy (E), and pre‐exponential factor (Z) increased with increasing DGEBA content from 50 to 80 wt % in the reactive blends and increased drastically above 70 wt % DGEBA content due to the higher crosslink density. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 687–697, 2004     

Mechanical properties,morphology, and crystallization behavior of new thermoplastic polyimide (N‐TPI)/poly(ether sulfone) blends

Blends of wholly aromatic new thermoplastic polyimide (N‐TPI) and poly(ether sulfone) (PES) were prepared by melt‐mixing and subsequent injection molding. Their mechanical properties, morphology, and crystallization behavior were investigated. A synergistic effect on the flexural properties was observed for the N‐TPI/PES blends over the whole compositions. Differential scanning calorimetric analysis confirmed that the blend is an immiscible system and that the crystallinity of the N‐TPI component is very low (0.4–1.4%) irrespective of the composition. Scanning electron microscopic analysis suggested that the improvement in flexural properties is likely due to the reinforcement of the PES matrix by the fibrous N‐TPI phase for the N‐TPI/PES (40/60, 20/80) blends. For N‐TPI/PES (80/20, 60/40), the orientation of the matrix N‐TPI rather than the fibrillation of the PES phase along the melt‐flow direction may contribute to the synergism observed. Also, study of the isothermal crystallization behavior of the blends revealed that the addition of 10 wt % PES accelerates the crystallization of N‐TPI and further addition causes the retardation of it. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1366–1374, 2002