Influence of binary combined systems of antioxidants on the stabilization of peroxide‐cured low‐density polyethylene

The secondary antioxidants Irganox 168 and 242 and dilaurylthiodipropionate (didodecyl‐3,3′‐thiodipropionate) (DLTP) were chosen to be combined with the primary phenol antioxidants Irganox 300, 1010, 1035, and 1076, and the effects of the binary combined systems of antioxidants on the peroxide curing reaction and the long‐term stability of crosslinked low‐density polyethylene (XLPE) were studied through isothermal dynamic rheological and mechanical testing. The results show that the primary phenol antioxidants with lower melting points had better resistance to scorching and exhibited good synergistic effects with the secondary antioxidants. Irganox 168 had little resistance to scorching, whereas Irganox DLTP had moderate resistance, and Irganox 242 had the greatest resistance. Irganox 168 and DLTP guaranteed the mechanical properties well, whereas Irganox 242 reduced the tensile strength obviously. Irganox 300 and 1035 combined with secondary antioxidants performed poorly in long‐term thermal aging test, whereas Irganox 1076 in combination with secondary antioxidants displayed a moderate effect of aging resistance, and Irganox 1010 showed the best effect. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Rheological investigation of cure kinetics and adhesive strength of polyurethane acrylate adhesive

In this work, we used rheological techniques to study both the cure characteristics and the degree of cure of polyurethane acrylate adhesive, a type of reactive adhesive used in hard disk component assembly. These results were then correlated with the tensile shear strengths of adhesives. Here, the cure characteristics of polyurethane adhesive were investigated at isothermal conditions ranging from 25 to 120°C. From the rheological results, the gelation time, the vitrification time, as well as the time required to reach the maximum degree of cure, decreased when increasing the curing temperature. The cure rates of adhesive increased with temperature in three temperature ranges, which were retardation zone, vitrification zone, and reaction‐controlled zone. The cure rates in these zones were controlled by slow diffusion, fast diffusion, and the rate of reaction, respectively. From the temperature sweep of fully‐cured adhesives, we found that the crosslinking level of adhesives increased with curing temperatures at different rates depending on the temperature zones as well. Moreover, the adhesive strength measured by tensile shear test was found to also increase correspondingly with the adhesives' T_g, indicating that the crosslinking level directly affected the adhesive strength. The strong dependence of adhesive strength with crosslinking level indicates that the crosslinking level was essential for high adhesive strength. The correlation of cure characteristics and adhesive strengths at various curing temperatures performed in this study can further provide useful information for planning appropriate curing schemes of polyurethane acrylate adhesives used in electronic and other industries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal cure behavior of unsaturated polyester/phenol blends

Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to detect and simulate the cure behavior of unsaturated polyester (UP), phenol, and UP/phenol blends and to calculate and predict the cure rate, cure temperature, conversion, and changes in the glass‐transition temperature along with various cure orders in order to obtain the optimum parameters for processing. With dynamic scanning and isothermal DSC procedures and Borchardt–Daniels dynamic software, cure data for the UP resin were obtained, 90% of the conversion rate at 100°C being achieved after 15 min. However, for the phenol and UP/phenol blends, gradually increasing the temperature was found to be best for curing according to the DSC and DMA test results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1041–1058, 2004     

A thermal and rheological investigation during the complex cure of a two‐component thermoset polyurethane

The complex cure kinetics of the reaction between oligomeric diphenylmethane diisocyanate (PMDI) and glycerol was characterized through thermal and rheological techniques. Isoconversional analysis of Differential scanning calorimetry (DSC) data resulted in the activation energy varying with conversion. Isothermal analysis gave activation energies ranging from 5 kJ/mol to 33.7 kJ/ mol, whereas nonisothermal data gave values for the activation energy ranging from 49.5 to 55 kJ/mol. Incomplete cure was evident in isothermal DSC, becoming diffusion controlled in the final stages of cure. DMA analysis on the cured material gave a glass transition temperature of 104 ± 3°C, which was evidence for vitrification of the curing system. The primary and secondary hydroxyl group reactivity was dependant on the isothermal cure temperature. Rheological studies of viscosity increase and tan δ changes with time revealed a complex cure process, with primary and secondary hydroxyl reactivity also showing dependence on isothermal cure temperatures, reflecting similar results obtained from isothermal DSC studies. The independence of tan δ on frequency was used to determine the point where the polymer formed an infinite network and was no longer able to flow, providing an overall activation energy attained at the gel point of 77.4 ± 4.4 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Analysis of the cure of epoxy based layered silicate nanocomposites: Reaction kinetics and nanostructure development

The cure reaction kinetics of epoxy resin, with organically modified montmorillonite loadings of up to 20 wt % and with stoichiometric conditions, has been studied by differential scanning calorimetry with a view to understanding further the fabrication of epoxy‐based polymer layered silicate nanocomposites. The kinetic analysis of isothermal and nonisothermal cure shows that the autocatalytic model is the more appropriate to describe the kinetics of these reactions, and it is observed that a dominant effect of the montmorillonite is to catalyze the curing reaction. However, it was not possible to model the reactions over the whole range of degrees of conversion, in particular for nonisothermal cure. This attributed to the complexity of the reactions, and especially to the occurrence of etherification by cationic homopolymerization catalyzed by the onium ion of the organically modified montmorillonite. The homopolymerization reaction results in an excess of diamine in the system, and hence in practice the reaction is off stoichiometric, which leads to a reduction in both the heat of cure and the glass transition temperature as the montmorillonite content increases. Small angle X‐ray scattering of the cured nanocomposites shows that an exfoliated nanostructure is obtained in nonisothermal cure at slow heating rates, whereas for nonisothermal cure at faster heating rates, as well as for isothermal cure at 70°C and 100°C, a certain amount of exfoliation is accompanied by the growth of d‐spacings of 1.4 nm and 1.8 nm for dynamic and isothermal cure, respectively, smaller than the d‐spacings of the modified clay before intercalation of the resin. A similar nanostructure, consisting of extensive exfoliation accompanied by a strong scattering at distances less than the d‐spacing of the modified clay, is also found for resin/clay mixtures, before the addition of any crosslinking agent, which have been preconditioned by storage for long times at room temperature. The development of these nanostructures is attributed to the presence of clay agglomerations in the original resin/clay mixtures and highlights the importance of the quality of the dispersion of the clay in the resin in respect of achieving a homogeneous exfoliated nanostructure in the cured nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Curing behavior of a novel polytriazole resin

The curing behavior of a novel low temperature curing polytriazole resin, prepared from p‐xylylene diazide and N,N,N′,N′‐tetrapropargyl‐p,p′‐diaminodiphenylmethane, was investigated by DSC and rheological analyses. The kinetics of the curing of the resin was studied by nonisothermal and isothermal DSC measurements and the kinetics parameters were obtained. The values of apparent activation energy E_a of the curing reaction obtained by nonisothermal and isothermal DSC are 80.7 and 75.3 kJ/mol, respectively. The curing of the resin was traced by the isothermal rheological analysis. The gelation times of the resin at 70, 75, 80, and 85°C are about 200, 150, 110, and 75 min, respectively. The viscosity equation for the resin was found as follows: © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Reversible crosslinked low density polyethylenes: structure and thermal properties

In the present study, low density polyethylene (LDPE) has been crosslinked at 170 °C with three different systems by a) using peroxide, b) peroxide and accelerator and c), peroxide, accelerator and sulfur. The effect of chemical crosslinking on LDPE structure has been investigated using torque measurements, Fourier transform infrared spectroscopy (FTIR), wide angle X-ray diffraction (WAXS), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Therefore, effects of each crosslinking system on the structural and thermal properties of the material in terms of crystallinity, thermal transitions and stability have been discussed. The reversible crosslinking of LDPE allow the recyclability of polyolefins, increasing the thermal properties.     

Cure kinetics of an epoxy resin containing naphthyl/dicyclopentadiene moieties and bis‐phenoxy (3‐hydroxy) phosphine oxide system and properties of its cured polymer

The cure kinetics of naphthyl/dicyclopentadiene epoxy resin and bisphenoxy (3‐hydroxy) phosphine oxide was investigated by differential scanning calorimetry (DSC) under nonisothermal and isothermal condition. The advanced isoconversional method was used to study the nonisothermal DSC data, the effective activation energy of the curing system in the early stage agreed with the value calculated from the Kissinger model and then increased because of the hindrance of molecular mobility. Autocatalytic behavior was shown in the isothermal DSC measurement, which was well described by Kamal model in the early curing stage. In the later stage, a crosslinked network structure was formed and the curing reaction was mainly controlled by diffusion. The diffusion factor was introduced to optimize the Kamal model and correct the deviation of the calculated data. The physical properties of the cured polymer were evaluated by dynamic mechanical thermal analyses, thermogravimetric analyses, and limiting oxygen index test, which exhibited relatively high glass transition temperature, thermal stability, and flame retardancy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of initiator on the curing of unsaturated polyester resin at 100 °C

Sheet molding compound (SMC) parts are fiber‐reinforced unsaturated polyester (UP) composites molded at 140–170 °C under a pressure of 60–100 bar. For economic and ecological reasons, the aim of this research project is to develop new SMC formulations to modify the molding conditions. For this, SMC formulations were modified and optimized to decrease the molding temperature to 100 °C. The strategy was to change the catalytic system (peroxides) in order to obtain highly reactive formulations at 100 °C. First, the temperatures of initiation of the reaction were determined by rheological and DSC measurements for each peroxide. Second, the UP resin crosslinking kinetics were measured for the various peroxides during an isothermal curing at 100 °C. The results obtained with the three experimental methods are compared and discussed. Finally, the laboratory analyses were validated by SMC molding trials. © 2019 Society of Chemical Industry     

Crystallization kinetics modeling of high density and linear low density polyethylene resins

This paper describes isothermal and nonisothermal crystallization kinetics of a Ziegler‐Natta catalyzed high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) resins. Standard techniques such as differential scanning calorimetry (DSC) and light depolarization microscopy (LDM) techniques were used to measure isothermal kinetics at low supercoolings. DSC was also used to measure nonisothermal crystallization kinetics at low cooling rates. Extrapolation of isothermal crystallization half‐times of Z‐N catalyzed LLDPE resin using the isothermal half‐time analysis led to erroneous predictions, possibly due to Z‐N LLDPE consisting of a mixture of molecules having different amounts of short chain branching (comonomer). However, predicted reciprocal half‐times at high supercoolings, using isothermal half‐time analysis and using nonlinear regression of nonisothermal crystallization kinetics measured at low cooling rates using the differential Nakamura model, of the HDPE were similar to measured reciprocal half times at high supercoolings of a similar HDPE by Patki and Phillips. It is also shown that the differential Nakamura model can be effectively used to model nonisothermal crystallization kinetics of HDPE resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of iPP crosslinking by means of dynamic and steady rheology measurements

The crosslinking of isotactic polypropylene (iPP) using crosslinking agents (CAs) based on a peroxide/sulfur/accelerator system is a very attractive new method that has been reported recently. The present work deals with the study of the dynamic rheological behavior of iPP during and after the crosslinking process. The influence of the CA concentration and the processing temperature T on the rheological behavior of the iPP was analyzed. The kinetics of the crosslinking reaction was established using the technique described by G. A. Harpell and D. H. Walrod. This reaction is found to be of order one. At T = 180°C, the crosslinking reaction was faster. By varying the crosslinking agent content, different crosslinking degrees of iPP, expressed by the corresponding gel content, are achieved. On the other hand, the modified polypropylene exhibits an unexpected viscosity‐shear rate pattern, which describes the reverse crosslinking reaction mainly occurring by the opening of the bridges of the new interpenetrating network (IPN) formed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cure kinetics of aqueous phenol–formaldehyde resins used for oriented strandboard manufacturing: Analytical technique

The cure kinetics of commercial phenol–formaldehyde (PF), used as oriented strandboard face and core resins, were studied using isothermal and dynamic differential scanning calorimetry (DSC). The cure of the face resin completely followed an nth‐order reaction mechanism. The reaction order was nearly 1 with activation energy of 79.29 kJ mol^?1. The core resin showed a more complicated cure mechanism, including both nth‐order and autocatalytic reactions. The nth‐order part, with reaction order of 2.38, began at lower temperatures, but the reaction rate of the autocatalytic part increased much faster with increase in curing temperature. The total reaction order for the autocatalytic part was about 5. Cure kinetic models, for both face and core resins, were developed. It is shown that the models fitted experimental data well, and that the isothermal DSC was much more reliable than the dynamic DSC in studying the cure kinetics. Furthermore, the relationships among cure reaction conversion (curing degree), cure temperature, and cure time were predicted for both resin systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1642–1650, 2006     

Polymer‐modified bitumen of recycled LDPE and maleated bitumen

Maleated bitumen was prepared by the reaction of penetration grade bitumen (80/100) with maleic anhydride at 150°C for 2 h under nitrogen atmosphere. The effectiveness of maleation was assessed in bitumen–recycled low‐density polyethylene (LDPE) blends in terms of their softening point and elastic recovery. It was observed that the softening point and elastic recovery of the blends increased after maleation of the base bitumen owing to the formation of an asphaltene‐linked‐LDPE system. To obtain the desired elasticity, a recoverable composition was worked out with the help of maleated bitumen, recycled LDPE and styrene–butadiene–styrene. The storage stability of the blends was assessed in terms of their difference in softening points, rheological parameters, and microstructure of the top and bottom portions of test tube samples. The difference in softening point of the recoverable maleated bitumen blend was 5°C as compared to 60°C for the base bitumen blend. The phase angle was also reduced to 7.4° at 70°C compared with the 44.30° for the base bitumen blend. Scanning electron micrographs indicate that polymers existed in both the top and the bottom portions of the aged test tube maleated blend samples. The stability of the blend was further improved when LDPE is colloidal milled with maleic anhydride in the blend preparation. Roofing bitumen was also made with maleated bitumen containing 9 wt % recycled LDPE content. Based on the rheological data, it was found that the maleated bitumen–LDPE blend exhibited superior time‐/temperature‐dependent response and higher creep recovery compared with the base bitumen blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Prediction of TMCH thermal hazard with various calorimetric tests by green thermal analysis technology

1,1,‐Di‐(tert‐butylperoxy)‐3,3,5‐trimethylcyclohexane (TMCH), a liquid organic peroxide, has been widely used in the chemical industry as a polymerization initiator. The thermokinetic parameters of TMCH are investigated by three types of calorimetric tests (isothermal, nonisothermal, and adiabatic) to determine thermal decomposition properties of TMCH using differential scanning calorimetry (DSC) isothermal tests, DSC nonisothermal tests, and vent sizing package 2 adiabatic tests, respectively. Comparisons of three kinds of thermal analysis models were done for kinetics simulation, which can result in a beneficial kinetic model and parameters of thermal decomposition of TMCH. The use of green technology to replace the complex methods and energy consumption of the traditional self‐accelerating decomposition temperature tests are discussed. There are significant disadvantages with traditional thermal analysis methods in terms of a novel, swift, and green technology, which is the achieved object here for preventing pollution and reducing energy consumption. © 2012 American Institute of Chemical Engineers AIChE J,, 2012     

Rheological,thermal, and morphological properties of low‐density polyethylene/ultra‐high‐molecular‐weight polyethylene and linear low‐density polyethylene/ultra‐high‐molecular‐weight polyethylene blends

The dynamic rheological behavior of low‐density polyethylene (LDPE)/ultra‐high‐molecular‐weight polyethylene (UHMWPE) blends and linear low‐density polyethylene (LLDPE)/UHMWPE blends was measured in a parallel‐plate rheometer at 180, 190, and 200°C. Analysis of the log–additivity rule, Cole–Cole plots, Han curves, and Van Gurp curves of the LDPE/UHMWPE blends indicated that the blends were miscible in the melt. In contrast, the rheological properties of LLDPE/UHMWPE showed that the miscibility of the blends was decided by the composition of LLDPE. The differential scanning calorimetry results and scanning electron microscopy photos of the LLDPE/UHMWPE blends were consistent with the rheological properties, whereas with regard to the thermal and morphological properties of LDPE/UHMWPE blends, the results reveal three endothermic peaks and phase separation, which indicated a liquid–solid phase separation in the LDPE/UHMWPE blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Click chemistry‐type crosslinking of a low‐conductivity polyethylene copolymer ternary blend for power cable insulation

High‐voltage direct‐current power cables are vital for the efficient transport of electricity derived from renewable sources of energy. The most widely used material for high‐voltage power cable insulation – low‐density polyethylene (LDPE) – is usually crosslinked with peroxides, a process that releases unwanted by‐products. Hence, by‐product‐free crosslinking concepts that mitigate the associated increase in electrical conductivity are in high demand. Click chemistry‐type crosslinking of polyethylene copolymer mixtures that contain glycidyl methacrylate and acrylic acid co‐monomers is a promising alternative, provided that the curing reaction can be controlled. Here, we demonstrate that the rate of the curing reaction can be adjusted by tuning the number of epoxy and carboxyl groups. Both dilution of copolymer mixtures with neat LDPE and the selection of copolymers with a lower co‐monomer content have an equivalent effect on the curing speed. Ternary blends that contain 50 wt% of neat LDPE feature an extended extrusion window of up to 170 °C. Instead, at 200 °C rapid curing is possible, leading to thermosets with a low direct‐current electrical conductivity of about 10^?16 S cm^?1 at an electric field of 20 kV mm^?1 and 70 °C. The conductivity of the blends explored here is comparable to or even lower than values measured for both ultraclean LDPE and a peroxide‐cured commercial crosslinked polyethylene grade. Hence, click chemistry curing represents a promising alternative to radical crosslinking with peroxides. © 2019 Society of Chemical Industry     

Phenol‐containing phthalonitrile polymers – synthesis,cure characteristics and laminate properties

Novolac–phthalonitrile polymers bearing a controlled concentration of phthalonitrile groups were synthesized by condensation of novolac with 4‐nitrophthalonitrile. The cure characteristics monitored by DSC and rheometry indicated acceleration of the cure reaction by the phenolic groups. Fourier transform infrared analysis of the cured products indicated that the cure mechanism was dependent on the extent of phthalonitrile substitution. In phenol‐rich systems, evidence was obtained for the phenol‐mediated reaction of nitrile groups resulting in the formation of isoindoline groups. The phthalonitrile‐rich system underwent crosslinking through formation of triazine and phthalocyanine groups. The phenol groups in the phthalonitrile backbone were conducive to building a stronger interphase in their carbon composites, resulting in better mechanical properties. This was corroborated by morphological studies by SEM. However, these groups were detrimental to the thermal stability of the cured resins. The polymers exhibited very high flame retardancy which improved further on increasing the degree of phthalonitrilation. Copyright © 2012 Society of Chemical Industry     

DSC and DMA studies on silane‐grafted and water‐crosslinked LDPE/LLDPE blends

Effects of silane grafting and water crosslinking reactions on crystallizations, melting behaviors, and dynamic mechanical properties of the LDPE/LLDPE blends are investigated using DSC and DMA. From DSC data, cocrystallization of LDPE and LLDPE does not occur, but cocrosslinking of these two polymers is evidenced at the experimental temperature of 100°C, a temperature lower than melting temperatures of both polymers. The water crosslinking reactions of the LLDPE‐rich blends enable development of a new phase having a melting endotherm in between that of LDPE and LLDPE. From the thermal fractionation data, interaction between LDPE and LLDPE is observed, and compatibilization of the blends can be achieved by the crosslinking reactions. From DMA data, the storage moduli of the blends are not found to be consistent with their degrees of crosslinking. The storage moduli of the blends are not simply determined by the degree of crosslinking but determined by very complicated but unclear factors. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1808–1816, 2001