Fracture behavior–morphology relationships in an unsaturated polyester resin modified with a liquid oligomer

An unsaturated polyester (UP) resin modified with a liquid polymer, polyoxypropylenetriamine (POPTA), at a concentration of 10 wt% has been precured at several temperatures. Phase separation takes place before gelation at all precure temperatures used. The glass‐transition region has been analyzed by dynamic mechanical analysis. Mechanical properties have been related to microstructural features. With a precure temperature fixed, the unsaturated polyester (UP) resin has also been modified with different contents of POPTA. Fracture toughness of the mixtures has also been analyzed and results are compared to those for the unmodified mixture. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1677–1685, 1999     

Relaxations during the postcure of unsaturated polyester networks by ultrasonic wave propagation,dynamic mechanical analysis,and dielectric analysis

Ultrasonic wave propagation, dynamic mechanical analysis, and dielectric analysis were used to monitor relaxation phenomena during the nonisothermal postcure of unsaturated polyester networks. The measurements covered 6 decades of frequency. As a result, the residual reactive groups, immobilized in the glassy state by vitrification during an isothermal cure step, gained molecular mobility, which promoted the formation of additional crosslinks. After the postcure, the reaction was complete, and the maximum achievable glass‐transition temperature was reached. Moreover, the frequency and temperature dependence of the two relaxations, one related to the glass‐transition temperature of the partially cured sample and the other to the glass transition of the fully cured sample, was evaluated. The Williams–Landel–Ferry equation was used to model the frequency dependence of the main α‐relaxation data obtained with the different techniques. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 596–602, 2005     

Synthesis and structure–property relationships of acrylic core–shell particle-toughened epoxy networks

The use of emulsion polymerization to prepare core–shell rubber (CSR) toughening particles with different shell thickness-to-core diameter ratios is described. The conditions leading to controlled particle size and morphology are discussed. The particle shell is crosslinked during the synthesis so that its integrity and morphology are maintained upon curing of the epoxy network. The mixing of the CSR particles with the reactive epoxy and the processing of toughened-epoxy networks are described. The characteristics of each phase and the mechanical properties of the materials are reported. The fracture parameters (K_lc, G_lc) are discussed in relation to the structure of the CSR-particles.     

Assessment of nanocomposites based on unsaturated polyester resin/nanoclay under impact loading

The aim of this study is to investigate the performance of nanoclay reinforced unsaturated polyester (UP) resin under impact loads. Nanocomposite specimens containing nanoclay in 0, 1.5, and 3 (wt%) were prepared by melt mixing method. X‐ray diffraction, transmission electron microscopy analysis, scanning electron microscope photographs, and viscosity changes in liquid state resin confirmed exfoliation and intercalation of the nanoclay in the UP resin system used. Tensile modulus showed an increase with increase in nanoclay content. However, the tensile strength and elongation at break exhibited reducing performance with increase in nanoclay content. Izod impact test results indicated better performance for the specimens containing nanoclay reinforcements, with 1.5 (wt%) of nanoclay specimens showing the highest value. High velocity impact tests were carried out using gas gun in velocity range of 20–100 m/sec and harden steel hemispherical tip projectile with diameter of 8.7 mm and weight of 11.54 g. Results for high velocity impact test indicated better performance by the specimens containing nanoclay, with 1.5 (wt%) nanoclay showing the highest attained value. Damage assessments of impact area for all specimens showed spalling type brittle failure with punch out and sever fragmentation pattern. Copyright © 2011 John Wiley & Sons, Ltd.     

The effects of monophenol chain terminators on the structure–property relationships of controlled epoxy networks

Five families of new controlled epoxy thermosets (CENs) using three monophenol chain terminators were prepared to study systematic changes in the structure and amount of the monophenol and the initial molecular weight between crosslinks (M_c,i) on the properties of epoxy thermosets. Glass transition temperature (T_g) decreases with monophenol mole fraction (χ) in proportion to both the concentration and flexibility of the chain terminator. Distinct serial relations for T_g depression were observed for the three M_c,i families. Dynamic mechanical analysis (DMA) shows significant perturbations of the relaxation behavior with added terminator as evidenced by decrease in peak tan δ and in post T_g damping. The rubbery coefficients of thermal expansion (CTE) increases with monophenol concentration only at χ > 0.05 and shows distinct curvature versus temperature, but is largely invariant with monophenol flexibility. The thermal stability of terminated CENs decreases only slightly with χ and little difference was found with monophenol structure. Most surprisingly, fracture toughness decreases markedly and discontinuously with χ depending on M_c,i. The values of the critical monophenol concentration at which fracture toughness markedly decreases (χ_c) are inversely proportional to M_c,i but are independent of monophenol flexibility. No correlation of χ_c with any of the calculated network structure parameters was apparent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1632–1640, 2008     

Nanotailoring of sepiolite clay with poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene]: structure–property correlation

Poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS)/sepiolite clay nanocomposites are prepared by solvent casting method. Two types of schemes have been adopted to establish the compatibility between nonpolar polymer (SEBS) and needle‐like inorganic filler (sepiolite), either by polar modification of the nonpolar polymer or organic modification of the inorganic filler. Structure–property correlation of nanocomposites derived from two different approaches is compared. Structural and morphological analysis of nanocomposites has been investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. Fourier transform infrared result shows better compatibility between SEBS and modified sepiolite clay compared to maleic anhydride grafted SEBS and pristine sepiolite in their nanocomposites. Tensile strength and % elongation are found to increase by 32 and 105%, respectively, with the addition of just 3 parts per hundred parts of resin (phr) modified sepiolite clay to pristine SEBS matrix. Moreover, thermal stability has also improved by 96°C with similar loading. This work provides a new insight into the structure and thermo‐mechanical properties of novel SEBS–sepiolite clay nanocomposites. Copyright © 2017 John Wiley & Sons, Ltd.     

The synthesis and properties of a reactive flame‐retardant unsaturated polyester resin from a phosphorus‐containing diacid

A transparent flame‐retardant unsaturated polyester resin (FR‐UPR) was obtained by reacting propylene glycol (PG) with maleic anhydride (MA), phthalic anhydride (PA), and 9,10‐dihydro‐10[2,3‐di(hydroxy carbonyl)propyl]‐10‐phosphaphenanthrene‐10‐oxide (DDP) synthesized from 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and itaconic acid (ITA). The chemical structure of the resulting FR‐UPR was confirmed by FTIR, ¹H‐NMR and ³¹P‐NMR. The average molecular weight and viscosity of the FR‐UPR were determined by gel permeation chromatography (GPC) and viscometer, respectively. Thermal stability was studied by thermogravimetric analysis (TGA) both in air and nitrogen to determine the thermal decomposition mechanism, and the apparent activation energy (E_a) was calculated by both the Kissinger and Ozawa methods. Compared to unsaturated polyester resin (UPR), the higher E_a of FR‐UPR3 implied an improved thermal stability. According to variations of the limited oxygen index (LOI) values, the UL 94 rating of vertical burning test and scanning electron microscopy (SEM) photographs of char residues, the flame retardance of cured FR‐UPR was enhanced with increasing DDP content. The study of fire reaction tests, using a cone calorimeter, suggested that there was a significant reduction of flammability in the FR‐UPR. Copyright © 2010 John Wiley & Sons, Ltd.     

BMD/UP体系非等温固化动力学研究

不饱和聚酯是最常用的一种热固性材料,其力学性能和耐热性是较受关注的两个方面,利用双马来酰亚胺作为第二组分对不饱和聚酯进行耐热改性的工作取得了较好的效果。研究其动力学过程对于固化反应温度、时间等工艺合理优化控制,制备高性能复合材料具有重要意义。考虑到BMD／UP体系中反应的复杂性,本文采用n级动力学模型,进行了非等温动力学研究。     

Synergistic effect of combined dimethyl methylphosphonate with aluminum hydroxide or ammonium polyphosphate retardant systems on the flame retardancy and thermal properties of unsaturated polyester resin

A series of flame-retardant unsaturated polyester resin (UPR) were prepared by the addition of dimethyl methylphosphonate (DMMP) with various amounts of aluminum hydroxide (ATH) or ammonium polyphosphate (APP) as the flame retardants. The combustion resistance effects of ATH/DMMP and APP/DMMP systems were evaluated by limiting oxygen index test and vertical burning test (UL-94). The thermal properties of UPR were investigated by thermogravimetric analysis. The structure of char was observed by scanning electron microscopy. DMMP incorporated with ATH or APP improved the flame retardancy and thermal properties of UPR. However, the fire-retardant mechanism of these two systems were different: The ATH/DMMP system provided synergistic effect in charring property of the UPR, produced great amount of residual char, and thus revealed the excellent flame retardancy. The APP/DMMP system further improved the flame retardancy of the UPR due to the change in the residual char structure rather than the increase in the production of char.     

Influence of glass transition temperature of crosslinked unsaturated polyester resin/styrene formulations on the final conversion after an isothermal curing at 100°C

SMC (sheet molding compound) is a composite based on fibers‐reinforced unsaturated polyester (UP) resin molded usually at 140°C to 170°C under a pressure of 60 to 100 bars. In order to develop new SMC formulations that can be molded at lower temperature (100°C) for economic and environmental reasons, the formulation of the composite had to be completely modified, both to allow a rapid reaction at 100°C, but also to avoid a vitrification phenomenon due to the fact that the glass transition temperature (Tg) of the SMC parts becomes, during the molding process, higher than the mold temperature. In this paper, the relation between the molding temperature, the glass transition temperature, and the final conversion of UP resin/styrene formulations has been underlined. The Tg of the cured resin was decreased by two different ways. The first way involved the reduction of the crosslinking density of the UP resin by using a blend of two resins, a pure maleic and a more flexible one. This blend allows to adjust the Tg over a temperature range from 197°C (Tg of the pure UP resin) to 75°C (Tg of the pure flexible resin). The second way consisted in the addition of butyl methacrylate (BuMA), a reactive plasticizer, to the formulation, allowing a decrease of the final material's Tg from 197°C to 130°C by replacing 35 wt% of styrene by BuMA. These two methods allow to obtain a final conversion of 99% after 8 minutes of molding at 100°C.     

Unsaturated polyester resins cure: Kinetic,rheologic, and mechanical dynamical analysis. II. The glass transition in the mechanical dynamical spectrum of polyester networks

Unsaturated polyester networks with various structures built from an orthophtalic polyester, with methyl ethyl ketone peroxide as an initiator and cobalt octoate as a promoter, were studied with dynamic mechanical thermal analysis from −50 to 200 °C to characterize changes in the mechanical properties as a function of the temperature. From these measurements, the glass‐transition temperatures of the different networks were determined, their dependence on conversion being fitted to an equation related to the Couchman and DiBenedetto equations. Finally, the different transitions were analyzed as a function of the cure conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 146–152, 2001     

Fluorinated benzoxazines and the structure‐property relationship of resulting polybenzoxazines

Three fluorinated benzoxazines ( 14–16 ), which cannot be synthesized by the traditional one‐step approaches, were synthesized by a three‐step procedure using fluorinated aromatic diamines ( 2–4 ) as starting materials. The structures of the monomers were confirmed by ¹H NMR, IR, and high‐resolution mass spectra. The low dielectric thermosets, P( 14–16 ), were prepared by ring‐opening of ( 14–16 ). IR analysis was utilized to monitor the ring‐opening reaction of ( 14–16 ) and to propose the structures of P( 14–16 ). The thermal and dielectric properties of P( 14–16 ) were studied and compared with a nonfluorinated polybenzoxazine P( 13 ), which is derived form the ring‐opening of 2,2‐bis(4‐aminophenoxy)phenyl)propane ( 1 ). Besides, the structure–property relationship of the P( 13–16 ) is discussed. According to T_g measurement, the ortho‐positioned CF₃ substituents impart greater steric hindrance for ring‐opening of benzoxazines than CF₃ substituents of hexafluoropropane. Incorporating a biphenol F‐based benzoxazine, ( F‐a ), into fluorinated benzoxazines ( 15–16 ) can dilute the effect of ortho‐positioned CF₃ substituents on steric hindrance, leading to a higher crosslinking density and consequently a higher Tg. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4970–4983, 2008     

Modified montmorillonite combined with intumescent flame retardants on the flame retardancy and thermal stability properties of unsaturated polyester resins

Modified montmorillonite‐containing phytic acid (PA‐MMT) has been prepared by acid treatment and then introduced into unsaturated polyester resin (UPR) with an intumescent flame retardant (IFRs). The flame retardancy and thermal degradation of UPR/IFRs/PA‐MMT were evaluated by a limiting oxygen index (LOI) test, a vertical burning test (UL‐94), a thermogravimetric analysis (TGA), and a cone calorimeter test (CCT). Besides, the mechanical properties were studied by a universal testing machine. The LOI value of UPR/IFRs/PA‐MMT composites was increased to 29.2%. The CCT results indicated that the incorporation of PA‐MMT and IFRs significantly improved the combustion behavior of UPR. The results of the mechanical properties indicated that 1.5 wt% loading of PA‐MMT in UPR/IFRs showed the highest improvement in flexural strength and tensile strength. The flame‐retardant mechanism of PA‐MMT/IFRs was examined and discussed based on the results of combustion behavior and char analysis.     

The effects of monoepoxide chain termination and their derived soluble fractions on the structure‐property relationships of controlled epoxy networks

A new series of monoepoxide terminated controlled epoxy networks (CENs) and a corresponding soluble fraction polymer (SFP) were prepared to further investigate the effects of chain termination on epoxy thermoset structure‐property relationships. CENs having an initial molecular weight between crosslinks (M_c,i) of ～3000 g/mol using phenylglycidyl ether (PGE) as the chain terminator have thermal and mechanical properties consistent with previously studied monophenol terminated CENs. Glass transition temperature (T_g) decreases monotonically with PGE concentration (ε), whereas fracture toughness decreases sharply at a critical PGE concentration (ε_c). A PGE terminated SFP was prepared corresponding to the soluble fraction expected for the CEN composition at ε_c. The SFP behaves as a weak antiplasticizer in these epoxy thermosets; T_g is reduced and follows the inverse rule of mixtures, and fracture toughness is slightly reduced. By difference it is inferred that most of the deterioration of epoxy thermoset properties resulting from incorporation of chain terminators above ε_c is a result of the presence of nonelastically active pendant chains and by the increase in M_c. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 72–79, 2009     

Time-temperature transformation (TTT) cure diagram of an unsaturated polyester resin

The curing of an unsaturated polyester resin was studied by differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), and Fourier-transform infrared spectroscopy (FTIR). The results are presented in the form of a time-temperature-transformation (TTT) diagram. The kinetic analysis was performed by means of the dynamic Ozawa method. This analysis was used to determine the curing times (t) at various conversions (α) and temperatures (T) (isoconversional lines ln t = A + E/RT). The equivalence of the Ozawa method and the isothermal isoconversional adjustment ln t = A + E/RT were demonstrated. The relationship between the glassy transition temperature (T_g) and the conversion α was determined by DSC. It was established that this relationship is one-to-one and independent of mass, initiation system, and curing temperature (T_c). The T_g-α relationship was adjusted using the DiBenedetto equations and heat capacity data. Using the T_g-α relationship and the isoconversional lines, the vitrification curve was determined and it was observed that the vitrification times obtained are consistent with those obtained experimentally when T_c = T_g. Gelation was determined by TMA, the material being considered gelled when it reached sufficient mechanical stability for the TMA measuring probe to become embedded in it. At that moment the conversion reached was determined by DSC. It was seen that the material always gels at constant conversion, regardless of the curing temperature. The gelation line (gel times) were traced from the corresponding isoconversional line. © 1997 John Wiley & Sons, Inc.     

A process–structure–property study of anisotropic PMDA-ODA films

A practical methodology for the correlation and prediction of the process–property performance of advanced materials is developed. The model polymer studied is PMDA-ODA polyimide. The connecting link between the process and the properties is the structural state of the polymer. An essential ingredient for a quantitative characterization of the system is a knowledge of its phase state and intrinsic molecular properties. The intrinsic molecular properties define the limiting performance properties available to the polymer. Anisotropic films and sheets produced by five different fabrication processes are examined. Maps of the molecular symmetry axis, the orientation function, and the thickness distributions of two 50-in.-wide sheets fabricated differently are measured nondestructively for process comparison. Four other film fabrication processes are examined and their three-dimensional orientation states determined and correlated. A three-dimensional orientation function triangular plot permits simultaneous representation of the different fabrication processes on the same figure and allows the investigator to choose the most economic and efficient fabrication route. The structure–property study includes the structural correlation and intrinsic molecular property determination of the anisotropic coefficient of thermal expansion (CTE), the anisotropic mechanical moduli and compliances, and the anisotropic dielectric constants. 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 777–788, 1997     

Neopenthyl glycol containing poly(propylene terephthalate)s: structure–properties relationships

Poly(propylene/neopenthyl terephthalate) random copolymers (PPT‐PNT) and poly(neopenthyl terephthalate) (PNT) were synthesized and subjected to molecular characterization. Afterwards, the polyesters were examined by TGA, DSC, andX‐ray. The copolymers, which displayed a good thermal stability, at room temperature appeared as semicrystalline materials: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of the melting temperature with respect to homopolymer PPT. XRD measurements allowed the identification of the PPT crystalline structure in all cases. Amorphous samples were obtained after melt quenching, with the exception of PPT‐PNT5, and an increment of T_g as the content of NT units is increased was observed due to the effect of the side methylene groups in the polymeric chain. The Wood equation described well T_g‐composition data. Lastly, the presence of a rigid‐amorphous phase was evidenced in the copolymers, whose amount depended on composition and on thermal treatment. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 170–181, 2008     

Effects of nano ZnO on strength and stability of unsaturated polyester composites

ZnO–glass fiber–unsaturated polyester composites have been prepared. On exposure to the metal halide lamp, their resistance to ultraviolet (UV) degradation is evaluated. Experimental results show that ZnO can reduce the UV degradation of the unsaturated polyester matrix. ZnO can significantly retard the UV degradation process of the matrix resin, and can also increase the impact strength of the composites under the experimental conditions. Differential scanning calorimetry (DSC) analyses also indicate that the addition of ZnO to unsaturated polyester may retard the crosslink process and catalyze the decomposition of the resin. However, after more than 40 hr of UV irradiation, it was crosslinked. SEM fracture morphology shows that nano ZnO could hinder crack growth and induce more cracks, and when the content of ZnO reaches 6 wt%, the impact fracture mechanism changes abruptly and plastic deformation appears, which indicates that 6 wt% for ZnO in unsaturated polyester could be considered as the critical content. Around the critical content, the particles are near enough to interact with each other and this results in the change of fracture mechanism. The results also indicate that the proper content of ZnO added into an unsaturated polyester could prolong the durability and lessen the reject rate of transparent glass fiber–polyester composites. Copyright © 2008 John Wiley & Sons, Ltd.     

Fabrication of diatomite‐based microencapsulated flame retardant and its improved fire safety of unsaturated polyester resin

To achive excellent fire resistance, new microcapsule flame retardants (DMCAD and DMPPD) were prepared using 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide combined with melamine cyanurate or melamine polyphosphate as the shell material and diatomite as the core material. The successful assembly of DMCAD and DMPPD was detailed characterized by Fourier transform infrared (FT‐IR) spectra, X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Meanwhile, the flame retardancy and thermal stability of the unsaturated polyester resin (UPR)/DMCAD and UPR/DMPPD composites were also studied. The addition of DMCAD and DMPPD effectively improves the flame retardance properties of UPR, and the effect of DMPPD was better. The limiting oxygen index (LOI) of UPR/DMPPD‐3 increased by 11.6% when compared with that of UPR, and the sample achieved V‐0 rating. Moreover, the peak heat release rate (pHRR) and the total heat release (THR) rate of UPR/DMPPD‐3 were reduced by 67% and 26%, respectively. Under nitrogen condition and air condition, UPR/DMPPD showed better thermal stability and char‐forming ability from the thermogravimetric (TG) results. Residual char of the UPR composites was systematically analyzed with SEM and XPS. Finally, the flame retardant mechanism of DMPPD was proposed.     

Effect of the initiator content and temperature on the curing of an unsaturated polyester resin

The influence of temperature and the initiator concentration on the curing of an unsaturated polyester resin was studied by means of differential scanning calorimetry (DSC) and Fourier‐transform infrared spectroscopy (FTIR). It was established that there is an isoconversional relationship of the type lnt = a − bln[I]₀ between the curing time, t, and the initial initiator concentration, [I]₀, at a given temperature. This relationship indicates that the degree of conversion curves vs. the logarithm of the curing time at different [I]₀ may be superposed by displacement relative to a reference curve. It was confirmed that the reaction mechanism varies throughout the whole curing process, although it does not vary with the temperature and the [I]₀ at each degree of conversion. It was established that there is a universal isoconversional relationship of the type lnt = d − bln[I]₀ + E/RT that expresses the dependency of the curing time on the temperature, T, and the [I]₀. The parameters a, b, and d depend on the reaction mechanism, and can be calculated on the basis of isothermal experiments at different temperatures and with different [I]₀. The adjustment lnt = d − bln[I]₀ + E/RT shows that there is an equivalence between the effect on the curing kinetics of the temperature and the initiator concentration. The same curing process can be achieved by using different combinations of curing temperatures and the [I]₀. In the two adjustments established, it is not necessary to know the reaction mechanism, and the only assumption made is that for a given conversion the reaction mechanism is invariant with respect to the [I]₀ and the temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 751–768, 1999