Effect of curing temperature on the morphology of unsaturated polyester resin blended with poly(vinyl acetate)

Phase separation of unsaturated polyester/styrene (UPE/styrene) resin blended with 5 and 10 wt% of poly(vinyl acetate) (PVAc) cured at various temperatures ranging from 75°C to 150°C was studied using low angle laser light scattering (LALS) and scanning electron microscopy (SEM). For UPE/styrene resin blended with 5 wt% PVAc cured at a temperature below 90°C, a discrete phase‐separated structure was observed. As curing temperature was raised above 90°C, SEM micrographs revealed that more and more cured UPE globules fused together with increasing curing temperature. The LALS intensity profile became broader with increasing curing temperature, indicating a less discrete phase‐separated structure at a higher curing temperature. As PVAc content was increased to 10 wt%, SEM micrographs revealed a co‐continuous phase‐separated structure. The LALS intensity decayed slowly from the center of the scattering pattern to a high scattering angle without the appearance of maximum scattering peak intensity. The morphology of the cured sample did not change too much with curing temperature for UPE/styrene resin blended with 10 wt% of PVAc.     

Optimum consolidation of all‐polyester woven fabric‐reinforced composite laminates by film stacking

This study involves the examination of all‐polyester composites prepared using the two‐step consolidation of lamina and composites. The raw materials in this process are poly(ethylene terephthalate) (PET) plain woven fabric, used as reinforcement, and biodegradable polyester, used as a matrix. First, the all‐polyester laminae were produced at various consolidation temperatures (200, 210, 220, and 230°C) with a holding time of 1 min. Then, all‐polyester composites were prepared at various consolidation temperatures (200, 205, 210, 215, and 225°C) with a 3‐min holding time, using all‐polyester laminae consolidated at 220°C. This study established that proper lamina preparation is necessary for preparing a good composite, and a method is proposed that allows a wide processing window for composite preparation. The method is validated through the results of tensile, flexural, and Izod impact tests of lamina and composites. The optimum consolidation temperature observed was 220°C for all‐polyester lamina and 200–215°C for all‐polyester composites. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

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     

Influence of post-curing temperature on the structure,properties, and adhesion of vinyl ester adhesive

Vinyl ester (VE) resins are widely used as thermoset adhesives in structural joints and composites, but complete curing under environmental conditions is not produced. The existing literature dealing with the effect of post-curing on the structure, viscoelastic, mechanical, and adhesion properties of VE resin is scarce. Therefore, in this study, VE resin was subjected to different post-curing temperatures (50–140 °C) for one hour, and the changes in structure and properties were assessed. The degree of cross-linking of the VE resin depended on the post-curing temperature and cure started to be completed above 100 °C, a temperature close to the glass transition temperature (115 °C) of the completely cross-linked polymer. Furthermore, gel formation in VE resin was evidenced for post-curing temperature below 100 °C. In order to fully cross-link the VE resin, post-curing at 140 °C for one hour was necessary, and it was evidenced by an increase in the glass transition temperature and in the mechanical properties; an increase in adhesion to cold rolled steel was obtained although the shear strength was lower than in the joint produced with the non-post-cured VE resin.     

Investigation of non-isothermal crystallization,dynamic mechanical and dielectric properties of poly(ether-ketone) matrix composites

ABSTRACT

Poly(ether-ketone)/hexagonal boron nitride (h-BN) composites reinforced with micrometer-sized h-BN particles were investigated. The composites exhibited glass transition temperature (T_g) and thermal stability over 160°C and 560°C, respectively. The melting point and peak crystallization temperatures of the composites decreased up to 17°C and 12°C, respectively. The linear CTE of the composites decreased both below and above the T_g. The storage modulus increased with increasing h-BN content at all temperatures (50–250°C). The composites possessed excellent dielectric properties with insignificant dispersion with increasing frequency. Thus, resultant composites are promising candidates for the printed circuit boards/electronic substrates.     

Thermal and electrical properties of epoxy composites at high alumina loadings and various temperatures

Epoxy microcomposites with high loading micro alumina (Al₂O₃, 100–400 phr) were prepared by casting method and their thermal and electrical properties were studied at temperatures from 25 to 150 °C. The electric resistance device and the dielectric electrode device were designed to measure the electrical properties of the composites. Thermogravimetric analysis (TGA) and scanning electron microscopic proves the homodispersion of Al₂O₃ microparticles in epoxy. TGA indicates that the temperature of 5 % weight loss of epoxy/Al₂O₃ (100 phr) composite is 366 °C, 34 °C higher than that of pure epoxy. Differential scanning calorimetry shows that the glass transition temperature of epoxy/Al₂O₃ composite (400 phr) increases to 114.7 °C, 9.2 °C higher than that of pure epoxy. Thermal conductivity test demonstrated that with increasing Al₂O₃ content at 25 °C, thermal conductivity of epoxy/Al₂O₃ composites increased to 1.382 W/(m K) which is 5.62 times that of pure epoxy. Electrical tests demonstrate that by increasing of Al₂O₃ content and temperature, the electric resistance and dielectric properties of the composites show great dependencies on them. Resistivities of all the specimens decreased with the increasing of temperature owing to the increasing molecular mobility in the higher temperature. Resistivity of pure epoxy at 25 °C is about 9.56 × 10¹⁶ Ω cm, about one order of magnitude higher than that of pure epoxy at 125 °C and two orders of magnitude higher than that of pure epoxy at 150 °C. These results can give some advice to design formulations for practical applications in power apparatus.     

Structure of the carbon chain polymer in unsaturated polyesters

The curing behaviour of thick laminates was simulated by curing thin polyester sections isothermally at various temperatures. Unsaturated polyesters with different ratios of styrene to unsaturations in the polyester were cured with benzoyl peroxide and subjected to hydrolytic degradation. The molecular size and structure of the carbon chain polymer was examined by size exclusion liquid chromatography and high resolution ¹³C FT n.m.r. analysis and was found to depend on the reaction temperature. The overall values of the molecular weights ranged from 12 000 to 36 000, which is a magnitude lower than those reported earlier. There was a similar tendency for molar ratios of styrene to unsaturations in the resin varying between 1.25 and 2.00. In the region 60°C–80°C the molecular weight increased with increasing temperature and then, from a maximum at 80°C–90°C, the molecular weight decreased with cure temperature. For the molar ratio of styrene to unsaturations of 2.25 the molecular weight decreased with increasing cure temperature. The average styrene sequence lengths were not found to deviate from the ratio expected from the stoichiometry in the resin before curing except for temperatures below 70°C and above 120°C.     

Curing of unsaturated polyester resins: Effects of comonomer composition. II. High-temperature reactions

The effects of comonomer composition of the curing kinetics of unsaturated polyester (UP) resins at 100–120°C were investigated by differential scanning calorimetry (DSC) and infrared spectroscopy (IR) over the entire conversion range. One commercial UP resin, UP2821, with 6.82 unsaturated C?C bonds per polyester molecule, was used. For styrene/UP2821 reactions, experimental results of the initial and maximum reaction rates by DSC at 100–120°C revealed that the styrene content, as well as the reaction temperature, would affect the formation of microgel structures. As the initial molar ratio of styrene to polyester C?C bonds increased, the styrene swelling effect could enhance the intramicrogel crosslinking reactions, while the styrene dilution effect could diminish the intermicrogel crosslinking reactions. The competition between the two reactions would depend on the reaction temperatures. Finally, a microgel-based reaction mechanism was proposed for the high temperature reactions. © 1993 John Wiley & Sons, Inc.     

Heat treatment effects on microstructure and mechanical properties of CVI SiCf/PyC/SiC composites with Cansas-Ⅲ SiC fibers

The microstructure and mechanical properties of CVI-Cansas-III/PyC/SiC composites were systematically investigated after heat treatment under high temperature argon atmosphere, ranging from 1000 °C to 1500 °C, for different time durations. The results showed that the Cansas-III fibres degraded with increasing heat treatment temperature, resulting in degradation of the fibre properties due to pyrolysis of the SiOC phase inside the fibres. The bending strength of the composites remained nearly constant upon heat treatment at 1000 °C and 1250 °C, while a decline in bending strength was observed upon increasing the heat treatment temperature and time, specifically at 1350 °C and above. Moreover, the composites maintained their pseudo-plastic fracture behaviour below 1450 °C, while displaying brittle fracture of the ceramic after 100 h of heat treatment at 1500 °C, due to the complete crystallisation of the fibres.     

Mechanical properties and biodegradability of green composites based on biodegradable polyesters and lyocell fabric

Green composites composed of regenerated cellulose (lyocell) fabric and biodegradable polyesters [poly(3‐hydroxybutyrate‐co‐3‐hydroxyvarelate) (PHBV), poly(butylene succinate) (PBS), and poly(lactic acid) (PLA)] were prepared by compression‐molding method. The tensile moduli and strength of all the biodegradable polyester/lyocell composites increased with increasing fiber content. When the obtained PLA/lyocell composites were annealed at 100°C for 3 h, the tensile strength and moduli were lowered despite the increase of degree of crystallization of the PLA component. The SEM observation of the composites revealed that the surface of the annealed composite has many cracks caused by the shrinkage of the PLA adhered to lyocell fabric. Multilayered PLA/lyocell laminate composites showed considerably higher Izod impact strength than PLA. As a result of the soil viral test, although the order of higher weight loss for the single substance was lyocell > PHBV > PBS > PLA, the biodegradability of the green composites did not reflect the order of a single substance because of the structural defect of the composite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3857–3863, 2004     

Some studies on thermal treatments of polyester fibers: Structural changes

The development of the changes of structure during thermal treatment of polyester fiber is studied. Critical dissolution time (CDT) was evaluated to trace the changes in crystallinity and crystal morphology of polyester fibers. CDT increased as the time of thermal treatment was increased. The change in CDT was less effective for samples thermally treated at temperatures up to 160°C, which may indicate a nucleation tendency of tiny crystals. CDT of polyester treated at 200°C in air was found to be relatively high, while silicon oil medium can affect both amorphous and crystalline regions, increasing the structure disorder. The effect of treatment under constant length revealed smaller CDT values than those attained by samples treated in free conditions. An indication to crystal size increase was traced by a decrease in peak width in X-ray diffraction pattern. Thermal treatment increased the crystallinity of polyester fibers up to 160°C. Dry air medium was more effective in increasing the disorder in amorphous regions than silicon oil medium. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2773–2780, 1997     

Determination of mechanical properties of glass‐epoxy composites in high temperatures

The objective of this study is to determine the tensile, compressive, and shear properties of unidirectional glass/epoxy composite plates under room (∼20°C) and high (40, 60, 80, and 100°C) temperatures. Mechanical properties were determined according to the ASTM standards. A hot lamination press was used for fabrication of composite plates. For curing process, laminated plates were retained at a constant pressure (250 kPa) and 120°C during 2 h. And then, composite plate is cooled to room temperature at the same pressure. The fiber volume fraction of laminated composite plate is measured as 65%. Experimental results show that the mechanical properties (except for the transverse tensile strength) of glass/epoxy composites are reduced by increasing temperature. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Surface‐modified sisal fiber‐reinforced eco‐friendly composites: Mechanical,thermal, and diffusion studies

To improve the fiber/matrix interaction, sisal fibers were subjected to various chemical and physical modifications such as mercerization, heating at 100°C, permanganate treatment, benzoylation, and silanization. Polyester composites were fabricated using compression molding. Tensile and flexural properties increased for every treated fiber‐reinforced composites with a reduction in the impact strength. This is attributed to the improved interfacial adhesion between fiber and polyester matrix. An increase in thermal stability was observed for the treated fiber‐reinforced composites especially at lower temperature. Significant reduction in water uptake occurred for the treated fiber‐reinforced composites at 30°C and 90°C. Scanning electron micrograph studies have been used to substantiate the above observations. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

The tribological properties of poly(p‐phenylene benzobisoxazole) pulp reinforced friction materials

Automotive friction materials reinforced by home‐made poly (p‐phenylene benzobisoxazole) (PBO) pulp (fibrillated organic fibers) were prepared through compression molding. The friction and wear behaviors of the obtained composite materials were evaluated using a constant rotating speed type friction tester. The PBO pulp content and the testing loads showed clear influence on the tribological properties of the composites. Friction stability, wear rate, and morphology of sliding surfaces were carefully examined to investigate the effect of the pulp ingredient in the friction materials. Scanning electron microscopy was employed to study the morphology of the surface and wear particles. The significant wear reduction was achieved when the mass fraction of PBO pulp was 3%. Wear rates of the composites with 3% PBO pulp were measured over a load range from 0.3 to 1 MPa at different temperatures. The results pointed to two facts: (1) the wear rate of the friction material increased linearly with load at low temperature (below 200°C); (2) wear status varied with the testing loads at high temperature (above 250°C). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4032–4039, 2013     

Kinetics of crosslinking of poly(vinyl chloride) in the presence of tetramethylthiuram disulfide and zinc oxide

Continuous measurements in a Vuremo curemeter at temperatures from 160°C to 195°C were used to estimate the extent of crosslinking of poly(vinyl chloride) which was plotted against cure time. The linearized forms of the cure curves clearly show that at obvious tetramethylthiuram disulfide–zinc oxide concentrations, the course of crosslinking differs significantly from the first-order rate law. These digressions caused by the degradation crosslinking of poly(vinyl chloride) were diminished by increasing tetramethylthiuram disulfide concentration, which simultaneously increases the ultimate extent of controlled crosslinking. On the basis of the above results, a method of the kinetic analysis of the cure curves is discussed.     

The influence of post‐cure on properties of carbon/phenolic resin cured composites and their final carbon/carbon composites

Two‐dimensional (2D) carbon/carbon (C/C) composites were prepared with phenol‐formaldehyde resin and graphite fabric. After curing, polymer composites were post‐cured in air at 160°C and 230°C for several hours and then all polymer composites were carbonized up to 1500°C. The effect of post‐cure on the microstructure and fracture behavior of the resultant carbon/carbon composites was studied. The post‐cure process was characterized by weight loss. This process promoted the crosslinking and condensation reactions and led to the formation of long‐chain, cross‐linked polymeric structures in the matrix. The post‐cured composites had a greater density than the unpost‐cured composite. This study indicates that a longer post‐curing time and higher post‐curing temperature would limit the shrinkage for the post‐cured composites during carbonization. The improvement in linear shrinkage was 22% to 44%. This process also limited the formation of open pores and decreased the weight loss of the resultant C/C composites. The resultant C/C composites developed from post‐cured composites had a greater flexural strength by 7 to 26% over that developed from unpost‐cured composite.     

Melamine as cross-linking agent for mono-cyclic benzoxazine with aldehyde groups: higher crosslinking density and thermal properties

Benzoxazine resin shows great potential as matrix for high performance composites, possessing good processabilty, dielectric property, mechanical property, and thermal properties, but its further application is limited by low crosslinking density and poor curing activity, especially for mono-cyclic benzoxazines. In this work, melamine, a tertiary amine with a stable triazine structure, was introduced into the aldehyde-containing mono-cyclic benzoxazine, in order to achieve higher crosslinking density, higher curing activity, and better thermal properties. The chemical structure of prepolymers was verified by Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance (¹H NMR) spectra, the curing behavior was investigated by differential scanning calorimetry, the thermal properties of polymers were studied by thermogravimetric analysis (TGA) and thermal mechanical analysis (TMA). It was found that the introduction of trifunctional melamine (MA) could lower curing temperature and promote the curing degree. Additionally, a proper amount of MA could increase the crosslinking density and thermal properties of the resultant polybenzoxazine. For example, poly(BZ-3MA) showed the highest thermal stability with the temperature at 5% weight loss (T_d5) of 415°C, carbon residue (Y_c) of 67.7%, 23°C, and 2.9% higher than those of poly(BZ). Moreover, the glass transition temperature of poly(BZ-5MA) reached 204.06°C, 36.51°C higher than that of poly(BZ).     

Effects of poly(vinyl acetate) and poly(methyl methacrylate) low-profile additives on the curing of unsaturated polyester resins. I. Curing kinetics by DSC and FTIR

The effects of two low-profile additives (LPA), poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) on the curing kinetics during the cure of unsaturated polyester (UP) resins at 110°C were investigated by using a differential scanning calorimeter (DSC) and a Fourier transform infrared spectrometer (FTIR). The effects of temperature, molar ratio of styrene to polyester CC bonds, and LPA content on phase characteristics of the static ternary systems of styrene–UP–PVAc and styrene–UP–PMMA prior to reaction were presented. Depending on the molar ratio of styrene to polyester CC bonds, a small shoulder or a kinetic-controlled plateau in the initial portion of the DSC rate profile was observed for the LPA-containing sample. This was due to the facilitation of intramicrogel crosslinking reactions since LPA could enhance phase separation and thus favor the formation of clearly identified microgel particles. FTIR results showed that adding LPA could enhance the relative conversion of polyester CC bonds to styrene throughout the reaction. Finally, by use of a microgel-based kinetic model and static phase characteristics of styrene–UP–LPA systems at 25°C, the effects of LPA on reaction kinetics regarding intramicrogel and intermicrogel crosslinking reactions, relative conversion of styrene to polyester CC bonds, and the final conversio have been explained. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of novel saponified guar‐graft‐poly(acrylonitrile)/silica nanocomposite materials

The combination of carbohydrates with silicon‐based ceramic materials offers attractive means of production for high performance materials. Present article describes the synthesis of novel nanocomposites out of SiO₂ and saponified guar‐graft‐poly(acrylonitrile) (SG). Tetraethoxysilane was used as the precursor for silica and growth of SiO₂ phase was allowed concurrently in the presence of SG. The material so obtained was thermally treated at 80°C, 160°C, 500°C, and 900°C to study the effect of thermal curing on its properties. During the curing process, silanol surface groups of silica globules reacted to create the reinforced SiO₂‐SG substance. It was observed that at 900°C, the SiO₂ phase crystallized out in tetragonal shape (similar to Cristobalite form of silica) in presence of SG. The chemical, structural and textural characteristics of the composites were determined by FTIR, XRD, TGA‐DTA, SEM and BET studies. The materials were also evaluated as efficient Zn²⁺ metal binder. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 536–544, 2007     

Modification of unsaturated polyesters by poly(ethylene glycol) end groups

This article reports on the modification of unsaturated polyesters by poly(ethylene glycol) end groups in order to influence the solution behavior in styrene and to modify mechanical properties of the cured resin. The synthesis was done by the reaction of a carboxyl-terminated unsaturated polyester with various poly(ethylene glycol) mono-methyl ethers of molecular weights from 350 to 2000 g/mol. The characterization and curing properties of the synthesized block copolymers are presented. The glass transition temperatures decrease with increasing length of the poly(ethylene glycol) end groups. The introduction of long poly(ethylene glycol) end groups (2000 g/mol) leads to a phase separated and partly crystalline block copolymer with a melting point of 48°C. The block copolymers can be easily diluted in styrene to create the curable resins. The mixtures containing the block copolymers with the short poly(ethylene glycol) end groups (350 and 550 g/mol) could be cured in a reasonably short time. Compared to commercial unsaturated polyesters the mechanical testing revealed that the tensile strength is decreasing while the elongation is increasing. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 527–537, 1997