Investigation of the thermal properties of novel adamantane‐modified polybenzoxazine

Two novel structures of adamantane‐modified benzoxazines were synthesized from 4‐(1‐adamantyl)‐phenol through the incorporation of adamantane as a pendant group into the polybenzoxazine backbone. Both ¹H‐NMR and Fourier transform infrared spectra were used to characterize these structures. The rigid structure of the adamantane tended to hinder the chain mobility (boat anchor effect) and substantially enhanced the thermal properties, including the glass‐transition temperature and decomposition temperature, especially for poly(6‐adamantyl‐3‐methyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine). In the poly(6‐adamantyl‐3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine) system, however, the opposite result for the glass‐transition temperature was observed and it was interpreted as lower crosslinking density. The phenyl group was bulkier than the methyl group, and the movement of the molecular chain was hindered between bridging points during the curing process; this resulted in a lower crosslinking density and a lower glass‐transition temperature than those of poly(6‐adamantyl‐3‐methyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 932–940, 2004     

Quasi‐isothermal DSC testing of epoxy adhesives using initial fast heating rates

Three major factors decrease the accuracy of the cure measurement in standard‐isothermal testing using differential scanning calorimetry (DSC). First, cure occurs during the heating step. Second, data are lost during the stabilization period between the dynamic and isothermal step. Third, the baseline selection requires a modification to the protocol. An alternative, which is explored in this study, is the use of fast ramps, which decrease the heating time, but this has been avoided due to overshoot that occurs between the dynamic and isothermal step, which is troublesome for systems with autocatalytic kinetics. By mitigating these factors, a quasi‐isothermal protocol was developed. Therefore, more complete cure kinetics were captured with the implementation of fast DSC to decrease the ramp time and through the optimization of furnace parameters to decrease stabilization time and temperature overshoot. The data suggested this quasi‐isothermal analysis more accurately measured the isothermal curing kinetics of a commercial epoxy adhesive at 110, 115, and 120 °C for fast ramps of 175, 350, and 500 K/min compared to the traditional ramp of 5 K/min. The enthalpy spike at the dynamic to isothermal transition remains an issue; however, an empirical shift can be used to compensate for the enthalpy signal lag. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45425.     

Aspects of reproducibility and stability for partial cure of epoxy matrix resin

Partial cure of thermosets is a promising approach to enhance manufacturing possibilities of reinforced and unreinforced polymers. If partial cure is taken into consideration as a genuine process parameter, novel manufacturing technologies can be developed by exploiting the specific properties of incomplete polymer networks. A main concern in this context is to control the kinetic reaction avoiding inhomogeneous or instable degrees of cure. Based on a combination of numerical simulations and experiments, a methodology is presented that enables a systematic assessment of the reproducibility and stability of partial cure. Special attention is paid to the interaction of thermal boundary conditions and the cure kinetic of thick samples as well as the storability of partially cured resin under different conditions. Guidelines for cure cycle selection, mold design, and storage are derived. The possibility to use complex multistep cure schedules and extended storage periods is demonstrated for an unmodified noninhibited epoxy resin. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals Inc. J. Appl. Polym. Sci. 2020 , 137, 48342.     

Intra‐ and extra‐gallery reactions in tri‐functional epoxy polymer layered silicate nanocomposites

Achieving a high degree of exfoliation in epoxy‐based polymer layered silicate (PLS) nanocomposites is crucial to their successful industrial application, but has hitherto proved elusive. In this work, a system is presented which shows significant promise in this respect. The isothermal cure of PLS nanocomposites based upon a tri‐functional epoxy resin (TGAP) has been studied by DSC, and displays two exothermic peaks. The first peak, very rapid, relates to a homopolymerization reaction within the intra‐gallery regions, while the second peak reflects the bulk crosslinking reaction. The occurrence of the intra‐gallery reaction before the bulk reaction enhances the degree of exfoliation in the cured nanocomposite. Furthermore, pre‐conditioning the resin/clay mixture before adding the curing agent and effecting the isothermal cure also allows a greater extent of intra‐gallery reaction to occur before the extra‐gallery epoxy‐amine reaction. Consequently, this system results in a high degree of exfoliation, as revealed by transmission electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhanced mechanical toughness of carbon nanofibrous-coated surface modified Kevlar reinforced polyurethane/epoxy matrix hybrid composites

High-performance Kevlar fiber had extensively been explored to upgraded mechanical properties of the advanced composites. Therefore, this study aimed a challenging work to grow carbon nanofibers onto the Kevlar fiber to improve its fiber-matrix interaction properties. It was successfully done through inexpensive flame deposition as well as modification of matrix with hybrid resin using polyurethane-epoxy mixture. A hand-layup method had been adopted to manufacture the composite laminates. The chemical and surface structures of the prepared laminae were examined by scanning electron microscopy, Raman spectroscopy, X-ray diffraction, and the composite's properties were evaluated tensile test, compact tension (CT) fracture test, fractography, and differential scanning calorimetry. The surface modified Kevlar laminae with CNF were used as reinforcing layer in the epoxy and PU/epoxy hybrid resin matrices. CNF-coated heated Kevlar reinforced laminated PU/epoxy hybrid composites (CNF-Kev/PU-Epoxy) showed highest elongation 47% and fracture toughness (11.7 MPa√m) along with good UTS 139 MPa. Therefore, these hybrid nanocomposites developed by simple inexpensive method would be the potential candidates for several advanced applications particularly in defense, automobile, aerospace, and spacecraft applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48802.     

State of the water in crosslinked sulfonated poly(ether ether ketone)

We investigated the material properties of different crosslinked sulfonated poly(aryl ether ketone) membranes, focusing on the effect of the degree of sulfonation and crosslinking density on the water uptake, the physical state of the water, and the pore size distribution within the membranes. We observed that the degree of sulfonation and, in particular, the ion‐exchange capacity (IEC) had less effect on the control of the extent of water absorbed than the crosslinking density of the membranes. Crosslinking also enabled the membranes to reach a higher water contents without losing mechanical integrity. Moreover, increasing the crosslinking density resulted in the presence of more bound water, without dissolution of the membrane. The crosslinked membranes had lower methanol permeability and electroosmotic drag values. Only at low IEC values and low water uptake in partially crystalline sulphonated poly(ether ether ketone), SPEEK could the presence of nanometer pores in the water‐equilibrated crosslinked membranes be confirmed by thermoporometry and the pore size distributions were then comparable to those reported for Nafion membranes. At higher IEC values, the water uptake was extremely high, up to 300%, and then the structure of the swollen membranes was more analogous to that of a dilute aqueous solution of the sulfonated polymer, and no nanopores were present. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Cure study of an acrylic resin to develop natural fiber composites

In the present study a new environmentally friendly acrylic resin was characterized to develop a high‐performance biocomposite for future work. Differential scanning calorimetry measurements were used to determine onset of curing reaction as well as the degree of cure at a certain temperatures. Swelling equilibrium data for an acrylic resin were generally analyzed using the Flory–Rehner equation for a perfect network, to obtain a measurement of the molar mass between two crosslinks and the crosslink density of polymer, and to establish the effect of temperature and time on these parameters. The crosslink density of cured resin at 180°C and 10 min indicates the completion of a major part of the reaction under those conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 757–762, 2004     

Correlation between viscoelastic behavior and cooling stresses in a cured epoxy resin system

This work deals with the study of the rheological behavior of an epoxy system subjected to three cooling processes referred to as the normal, air‐, and water‐cooling processes. The system was set up by a difunctional epoxy resin (DGEBA) mixed with a tetrafunctional diamine (mPDA) in stoichiometric proportions. Different samples of (1) neat and cured polymers and (2) alumina—epoxy composites were prepared. The first part of this work was devoted to optimizing the cure cycle of the neat samples using differential scanning calorimetry and rheometry. The best cure cycle is based on a first heat step at 110°C during 10 min followed by a crosslinking stage of 75 min at 180°C. In the second part of the study the influence of the cooling cycle on the thermomechanical behavior of polymer and composite samples was investigated. Measurement of loss modulus, G″, and loss factor, tan δ, versus temperature showed that an intermediate relaxation α′ peak arose between the main and secondary relaxations (resp. α and β). The position and amplitude of the α′ peak increased with the cooling rate. This rheological phenomenon is related to the presence of nonequilibrium stresses frozen in the sample during cooling. The effect of thermal aging on the α′ peak also is reported. Our work also showed the presence of an α′ peak for the composites. However, the amplitude of this peak was more pronounced in the composites because of additional stresses induced by the difference between the resin and the ceramic in thermal expansion coefficients. We showed that a calculation based on a thermoelastic model was useful for qualitative comparison of rheological data on the influence of the cooling process. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 679–690, 2006     

Influence of diaminobenzoyl‐functionalized multiwalled carbon nanotubes on the nonisothermal curing kinetics,dynamic mechanical properties,and thermal conductivity of epoxy–anhydride composites

To obtain advanced materials with a high thermal dissipation, the addition of multiwalled carbon nanotubes containing diverse functionality groups, that is, as‐received multiwalled carbon nanotubes (AS‐MWCNTs) and diaminobenzoyl multiwalled carbon nanotubes (DA‐MWCNTs), to epoxy–anhydride composites was accomplished. According to nonisothermal differential scanning calorimetry analysis, the reactive functional groups present on the surfaces of the AS‐MWCNTs and DA‐MWCNTs accelerated the nucleophilic addition reaction of epoxy composites. Because of the difference in the reactivities of these functional groups toward epoxy groups, the distinction of fractional conversion and the reaction rate of the curing process were remarkably evident at the early stage. A suitable kinetic model was effectively elucidated with the Málek approach. The curing kinetics could best be described by a two‐parameter autocatalytic model as a truncated ?esták–Berggren model. The DA‐MWCNTs achieved effective load transfer and active heat conductive pathways; this resulted in good dynamic mechanical and thermal properties. As a result, the diglycidyl ether of bisphenol A/DA‐MWCNTs constituted an effective system with enhanced heat dissipation of materials for electronic applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43567.     

The crosslinking of poly (ether ether ketone): Thermally and by irradiation

Crosslinking of amorphous poly (ether ether ketone) films was carried out by means of thermal annealing at 400°C as well as by irradiation with 11.0 MeV proton beam at different dose rate ranging from 1.75 to 15.5 kW g^?1. The materials properties of the resulting films were investigated by mean of light microscopy, sol‐gel analysis, two‐dimensional infra‐red correlation spectroscopy, 2DCOS‐IR, and differential scanning calorimetry (DSC). It was found that both chain scission and crosslinking yields were decreased by an increase of dose rate and the ratio of crosslinks to chain scission was increased from 0.9 to 1.4. The 2DCOS‐IR analysis in the region 1400–1800 cm^?1 showed progressive development of new bands at 1470 and 1740 cm^?1, which have been used to support the presence of crosslinking and chain scission reactions. The glass transition temperature also increased in line with increasing crosslinking density, but the results showed a limiting plateau value for the glass transition , which depended only on the absorbed dose. This suggests that crosslinking was limited and did not increase after a specific value of the dose rate. Crosslinking by irradiation has many advantages over thermal annealing; in particular it is a one step rapid process producing a variety of homogeneously crosslinked, good quality films available for chemical modification. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41999.     

Reactive blending approach to modify spin‐coated epoxy film: Part II. Crosslinking kinetics

Kinetics of the reactive blending of epoxy with a four‐armed ?‐caprolactone‐based carboxylic acid end‐functionalized oligomer was analyzed with a model‐free approach. The employment of a dual catalyst system ensured high density of crosslinking in the blends and minimized phase separation even when comparatively high concentration of the oligomer was incorporated. The two reactions were examined separately before analysis of the dual‐catalyzed system. The apparent activation energy of the single‐catalyzed reactions could be seen to fall into three regimes. It is proposed that regime I is due to reaction control, the middle part (II) to mass transport, and the high conversion tail (III) to structural control. The results of a thermal analysis carried out on the crosslinked samples corresponded well with the findings of the kinetic analysis. The combined kinetic and thermal results can be used in optimization of the crosslinking process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3689–3696, 2006     

A study about the structure of vulcanized natural rubber/styrene butadiene rubber blends and the glass transition behavior

A study of the thermal behavior of cured elastomeric blends of natural rubber (NR) and styrene butadiene rubber (SBR) prepared by solution blending in toluene is presented. Binary blends with different compositions of NR/SBR were produced using a conventional cure system based on sulfur and TBBS (n-t-butyl-2-benzothiazole sulfonamide as accelerator. The compounds were vulcanized at 433 K up to an optimum time of cure determined by rheometric tests. From swelling tests, the crosslink densities of the compounds were obtained and compared with those obtained in similar blends prepared by mechanical mixing. The results were analyzed in terms of the disentangling of the chain structures of the SBR and NR phases and the achieved cure state of the blend. Using differential scanning calorimetry, the glass transition temperature T_g of each blend was measured. In most compounds, the value of T_g corresponding to each phase of the blend was determined, but in some blends a single value of T_g was obtained. The variation of T_g with the composition and cure level in each phase was analyzed. On the other hand, a physical mixture of two equal parts of NR and SBR vulcanized was measured and the results were compared to those of the NR50/SBR50 cured blend. Besides, to analyze the influence of the network structure, pure NR and SBR unvulcanized samples were measured. On the basis of all the obtained results, the influence of the interphase formed in the blend between SBR and NR phases is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dynamics and thermal properties of epoxy resin cured by new diamino disiloxanes

Two disiloxane compounds, 3,3′‐(1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediyl)bis(benzenamine) ( C1 ) and 4,4′‐(1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediyl)bis(benzenamine) ( C2 ) were synthesized and used as new curing agents of DGEBA epoxy resin with an epoxy value of 0.51 ( E‐51 ). The curing kinetics of E‐51/C1 and E‐51/C2 systems was investigated by non‐isothermal differential scanning calorimetry (DSC) analyses. The activation energy (ΔE) and the characteristic cure temperatures of the two systems were determined. The two systems have the similar activation energy. The reactivity of E‐51/C1 is higher than that of E‐51/C2 . The reaction orders of E‐51/C1 and E‐51/C2 are 0.88 and 0.87, respectively, illustrating that curing reaction between the epoxy resin and curing agent ( C1 or C2 ) is complicated. The DSC result shows that E51 cured by C2 has higher Tg; whereas thermogravimetric analysis results indicate that E51 cured by C1 has higher thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42385.     

Melt functionalization of LDPE with thio ester,amino ester,and hydroxy ester by thermolysis method—An FTIR study

Low density poly(ethylene) (LDPE) was melt functionalized with three different esters namely, thio ester, amino ester, and hydroxy ester under inert atmosphere at 160°C with different experimental conditions. During the functionalization reaction, crosslinking (C.L) and C?C formation are the simultaneous competitive reactions. FTIR‐RI analysis method was used to determine the % functionalization onto LDPE backbone and the order of functionalization reaction. Thermogravemetric analysis (TGA) and Differential scanning calorimetry (DSC) were used to assess the thermal properties of the functionalized LDPE. Suitable reaction scheme was proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of cyanate ester modified by epoxy resin and phenolic resin

Stiff and brittle cyanate ester (CE) resin was modified by copolymerizing it with epoxy resin (ER) and phenolic resin (PR) to improve its toughness and flexibility. The cure process of the modified CE resin was characterized by gel time curves and differential scanning calorimetry curves. The Fourier transform infrared spectra of the modified CE resin showed its chemical structure during the curing process. The mechanical properties, thermal behavior, dielectric properties, and morphology of the modified CE resins were investigated. The results showed that an increase in epoxy and phenolic resins resulted in improved flexibility while maintaining thermal stability. When the mass ratio of CE/ER/PR was 70 : 15 : 15 (w/w), flexural strength and impact strength of the modified CE resin increased from 113.6 MPa and 5.2 kJ/m² to 134.5 MPa and 16.7 kJ/m², respectively. Little of the thermal stabilityand dielectric properties was sacrificed in the modification of the CE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3150–3156, 2007     

Reaction kinetics,thermal properties of tetramethyl biphenyl epoxy resin cured with aromatic diamine

Epoxy resins, 4, 4′‐diglycidyl (3, 3′, 5, 5′‐tetramethylbiphenyl) epoxy resin (TMBP) containing rigid rod structure as a class of high performance polymers has been researched. The investigation of cure kinetics of TMBP and diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) cured with p‐phenylenediamine (PDA) was performed by differential scanning calorimeter using an isoconversional method with dynamic conditions. The effect of the molar ratios of TMBP to PDA on the cure reaction kinetics was studied. The results showed that the curing of epoxy resins contains different stages. The activation energy was dependent of the degree of conversion. At the early of curing stages, the activation energy showed the activation energy took as maximum value. The effects of rigid rod groups and molar ratios of TMBP to PDA for the thermal properties were investigated by the DSC, DMA and TGA. The cured 2/1 TMBP/PDA system with rigid rod groups and high crosslink density had shown highest T_g and thermal degradation temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characterization of novel crosslinked poly[glycidyl methacrylate–poly(ethylene glycol) methyl ether methacrylate] as gel polymer electrolytes

In this study, glycidyl methacrylate was copolymerized with poly(ethylene glycol) methyl ether methacrylate to obtain a copolymer {poly[glycidyl methacrylate–poly(ethylene glycol) methyl ether methacrylate] [P(GMA–PEGMA)]}, which was crosslinked with α,ω‐diamino poly(propylene oxide) (Jeffamine) at various weight ratios and molecular weights to form novel gel polymer electrolytes (GPEs). The crosslinked copolymers were characterized by Fourier transform infrared spectroscopy and thermal analysis. The crosslinked polymers were amorphous in the pristine state and became crystallized after they were doped with lithium electrolyte. Furthermore, the crosslinking degree of the crosslinked polymers increased with increasing weight ratio of Jeffamine, and both the swelling properties and mechanical behaviors of the crosslinked polymers were heavily affected by the weight ratio and molecular weight of Jeffamine. The ionic conductivity (σ) of the GPEs from the crosslinked copolymers was determined by alternating‐current impedance spectroscopy. A higher molecular weight and increased weight ratio of Jeffamine resulted in a higher σ. The GPE based on P(GMA–PEGMA) crosslinked with an equal weight of Jeffamine D2000 exhibited the highest σ of 8.29 × 10⁻⁴ S/cm at 25°C and had a moderate mechanical strength. These crosslinked copolymers could be potential candidates for the construction of rechargeable lithium batteries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polyethylene glycol acrylate crosslinking copolymer as solid–solid phase change materials

A kind of crosslinking copolymer as solid–solid phase change material (PCM) is synthesized by copolymerization. The scope of PCM applications is often severely limited by their heat stablility and phase transition state. The solid–solid phase change materials we obtained retain basic state during phase change transitions. The crosslinking polymer is heat stable under 300° and the latent heat of crystalline and latent heat of melting is on the average of 120 J/g and 140J/g, respectively. The property of thermal stability and heat storaged is related to crosslinking density of the gel. The property of thermal stability and high latent heat may expand the scope of PCMs applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39755.     

Novel amphiphilic polymer gel electrolytes based on (PEG‐b‐GMA)‐co‐MMA

Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF₆ 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10^?4 S/cm at 25^oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Curing behavior of epoxy resins in two‐stage curing process by non‐isothermal differential scanning calorimetry kinetics method

In this research, a new thermal curing system, with two‐stage curing characteristics, has been designed. And the reaction behaviors of two different curing processes have been systematically studied. The non‐isothermal differential scanning calorimetry (DSC) test is used to discuss the curing reaction of two stages curing, and the data obtained from the curves are used to calculate the kinetic parameters. Kissinger‐Akahira‐Sunose (KAS) method is applied to determine activation energy (E_a) and investigate it as the change of conversion (α). Málek method is used to unravel the curing reaction mechanism. The results indicate that the curing behaviors of two different curing stages can be implemented successfully, and curing behavior is accorded with ?esták‐Berggren mode. The non‐isothermal DSC and Fourier transform infrared spectroscopy test results reveal that two different curing stages can be implemented successfully. Furthermore, the double x fitting method is used to determine the pre‐exponential factor (A), reaction order (m, n), and establish the kinetic equation. The fitting results between experiment curves and simulative curves prove that the kinetic equation can commendably describe the two different curing reaction processes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40711.