Straining phenomena of POY revealed by thermal retraction and other techniques

Partially oriented polyesters yarns (POY) were strained at different strain rates (0.03–12.00 min^?1) and temperatures above and below T_g (3–92°C). Thermal retraction, density, DSC, and WAXS techniques show that strain-induced crystallization takes place by straining at temperatures above as well as below T_g. Above T_g, depending upon the strain rate, two regimes are observed: Below the strain rate of 1.5 min^?1, the flow regime; the degree of crystallinity is reduced as the strain rate increases. Above the strain rate of 1.5 min^?1, the strain-induced crystallization regime; the degree of crystallinity increases as the strain rate increases. Thermal retraction, stress–relaxation, and sonic modulus techniques indicate that, upon cold straining, instead of the original T_g at 65–69°C, two glass transitions occur: an upper T_g (u) and a lower T_g (l). For POY strained at 3°C and at a strain rate of 10 min^?1, the values are 78°C and 37°C, respectively. The higher the strain rate and the lower the straining temperature, the large the difference between T_g (u) and T_g (l).     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Effect of heat treatment on the surface chemical structure of glass: Oxygen speciation from in situ XPS analysis

Compositional changes in unleached and acid‐leached soda‐lime silicate surfaces were tracked with in‐vacuo heating and X‐ray Photoelectron Spectroscopy. Surface oxygen speciation was determined using a stoichiometry‐based algorithm via elemental composition, instead of the typical O 1s peak‐fitting approach. Accurate surface hydroxyl quantification is shown to require dehydration at temperatures near 200°C. On the unleached surface, no change in surface hydroxyl density (~2.5 OH/nm²) is observed in the temperature range of 200°C‐500°C after the initial dehydration. However, repolymerization in the network (non‐bridging oxygen→bridging oxygen) is observed due to volatilization of sodium. The acid‐leached surface undergoes sodium out‐diffusion from the bulk at sub‐T_g temperatures with laterally resolved inhomogeneity and shows a reduction in the concentration of hydroxyls from 4.5 OH/nm² (200°C) to 3.2 OH/nm² (500°C) accompanied by an increase in bridging oxygen. These results suggest that when [OH] > 2.5~3/nm², vicinal OH undergo dehydroxylation with evolution of water, whereas when [OH] < 2.5/nm², most OHs are non‐interacting and isolated (at temperatures below T_g). Furthermore, at temperatures exceeding 300°C, sodium has enough thermal energy to desorb in vacuum and diffuse from the bulk (depending on the abundance & local structure).     

Study of the characterization and curing of benzoxazines using 13C solid-state nuclear magnetic resonance

Benzoxazines derived from bisphenol-A, formaldehyde, and primary amines were characterized using ¹³C solid-state NMR spectroscopy. The two 1,3-benzoxazines studied in this work are 2,2′-(3-methyl-4-dihydro-1,3,2-benzoxazine)propane, ( B-m ) and 2,2′-(3-phenyl-4-dihydro-1,3,2-benzoxazine)propane ( B-a ). Solid-state ¹³C-NMR spectra were obtained for B-m and B-a and the observed peak positions were noted. These resonances agreed well with chemical shifts calculated based on the chemical structure. Samples of B-m and B-a were cured at two different temperatures: 150 and 200°C. The polymerizations induced spectral changes including new resonances, intensity changes, and line-width broadenings. Kinetic analysis of the curing data gave different kinetic parameters for the two cure temperatures, which is expected since the first cure temperature is below the material's glass transition temperature (T_g) while the second cure temperature is above the T_g. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1413–1425, 1998     

Preparation and properties of rigid polyimide foams derived from dianhydride and isocyanate

A series of rigid polyimide (PI) foams were synthesized via the reaction of a first solution with a second solution. The first solution was isocyanate‐terminated polyimide prepolymers; the second solution contained deionized water and surfactant. The effect of different water contents and isocyanate index on the structures and properties of rigid PI foams were investigated. The apparent density, hardness, compressive strength, and the 5% weight loss temperatures (T_5%) decreased with the increase of water content. With the increase of isocyanate index, the apparent density and the T_5% values decreased, whereas the glass transition temperatures (T_g) increased and the hardness, compressive strength first increased and then decreased. The rigid PI foams composed of closed‐cells were confirmed by scanning electron microscopy. The maximum compressive strength of rigid PI foams prepared was up to 1.31 MPa. Moreover, excellent thermal stability was presented with the T_5% values were all above 360°C and the residual weights of the foams (R_w) were more than 50% at 800°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polyurethane networks from formiated soy polyols: Synthesis and mechanical characterization

Polyurethanes can be prepared using polyols obtained from vegetable oils in natura, such as castor oil, or from functionalized vegetable oils, such as hydroxylated soybean oil. These polyurethanes have different valuable properties, determined by their chemical composition and cross-linking density. In this study, soy epoxy polyols with different OH contents were prepared through a one-step reaction using the method of in situ performic acid generation. Polyols with OH functionalities from 1.9 to 3.2 were reacted in bulk with different diisocyanates at a NCO/OH molar ratio of 0.8 and 60°C for 24 h. Mechanical properties of the polyurethanes were determined by dynamic mechanical thermal analysis, hardness (Shore A), and swelling measurements. Polymer networks with glass-transition temperatures (T _g ) from −13 to 48°C were obtained. We observed that the higher the OH functionality of the polyols, the higher the T _g and cross-linking density of the polyurethane network. The influence of diisocyanate structure (rigid or flexible chain), curing temperature, and curing reaction time on mechanical properties was also investigated.     

Hydrolysis and blistering of cyanate ester networks

The hydrolysis of a cyanate ester network made from the monomer 2,2′-bis(4-cyanatophenyl) isopropylidene (bisphenol A dicyanate homopolymer) was studied. Hydrolysis reactions were performed isothermally at temperatures from 150 to 180°C under conditions of excess water. The kinetics of the reaction were characterized by the decrease in T_g as measured by differential scanning calorimetry. The rate of change of T_g was found to be adequately described as first order in T_g, which is an indirect measure of the concentration of crosslink junctions. The activation energy of the reaction was found to be 115 kJ/mol. In addition, moisture-conditioned, glass-reinforced laminate samples were heated and the time to delamination or blistering was recorded as a function of temperature. The blister time at solder temperatures (T = 220–260°C) was modeled using the above kinetic results. Heat transfer to the laminate was considered and the criteria used for blister time was the time at T = T_g of the sample. At lower temperatures (T < 220°C), loss of water from the laminate is sufficiently fast to prevent blistering. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 107–113, 1997     

Time-temperature–transformation (TTT) diagrams of high Tg epoxy systems: Competition between cure and thermal degradation

The cure behavior and thermal degradation of high T_g epoxy systems have been investigated by comparing their isothermal time-temperature-transformation (TTT) diagrams. The formulations were prepared from di- and trifunctional epoxy resins, and their mixtures, with stoichiometric amounts of a tetrafunctional aromatic diamine. The maximum glass transition temperatures (T_g∞) were 229°C and > 324°C for the fully cured di- and trifunctional epoxy materials, respectively. Increasing functionality of the reactants decreases the times to gelation and to vitrification, and increases the difference between T_g after prolonged isothermal cure and the temperature of cure. At high temperatures, there is competition between cure and thermal degradation. The latter was characterized by two main processes which involved devitrification (decrease of modulus and T_g) and revitrification (char formation). The experimentally inaccessible T_g∞ (352°C) for the trifunctional epoxy material was obtained by extrapolation from the values of T_g∞ of the less highly crosslinked systems using a relationship between the glass transition temperature, crosslink density, and chemical structure.     

Morphology,rheology, and mechanical properties of dynamically cured EPDM/PP blend: Effect of curing agent dose variation

The structure development, rheological behavior, viscoelastic, and mechanical properties of dynamically cured blend based on the ethylene–propylene–diene terpolymer (EPDM) and polypropylene (PP) with a ratio of 60/40 by weight were studied. The variation of two‐phase morphology was observed and compared as the level of curing agent was increased. Meanwhile, as the level of curing agent increased, viscosity as a function of shear stress always increased at a shear stress range of 2.2 × 10⁴ to 3.4 × 10⁵ Pa at the temperature of 200°C, yet viscosity of the blend approached each other at high shear stress. Dynamic mechanical spectra at different temperatures show that dynamic modulus (E′) of the blend exhibits two drastic transitions corresponding to glass transition temperature (T_g) of EPDM and T_g of PP, respectively. In the blends T_gs of EPDM increase and T_gs of PP almost remain unchangeable with an increase in curing agent level. Tensile strength increased, yet elongation at break decreased as the level of curing agent is increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 357–362, 2004     

Low temperature cure of epoxy thermosets attaining high Tg using a uniform microwave field

It is demonstrated for the first time that an epoxy thermoset resin can be cured at temperatures well below its T_g∞. This study compared the use of a uniform variable frequency microwave (VFM) field to standard oven curing at temperatures above and below T_g∞. Using T_g, tan δ, modulus, and FTIR measurements, it is shown that the reaction of BFDGE with MDA to attain a product with T_g∞ of 133 °C is achieved by VFM at temperatures from 100 to 140 °C; in contrast, the thermal cure normally requires 170 °C to attain the same T_g∞ and the same extent of cure. By following the pregel cure reaction with ¹³C‐NMR spectroscopy, it was determined that the lower cure temperatures of VFM cure predominately lead to chain extension and smaller amounts of crosslinking compared to the thermal cure. To explain these results, it is suggested that, after gelation, with VFM cure there is higher mobility from dipole rotations that continues the cure to completion without vitrification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44222.     

Transparent and organosoluble cardo polyimides with different trans/cis ratios of 1,4‐diaminocyclohexane via aromatic nucleophilic substitution polymerization

Two series of cardo polyimides were prepared from 1,4‐bis(4‐fluorophthalimide)cyclohexane with different trans/cis ratios and phenolphthalein/o‐cresolphthalein via aromatic nucleophilic substitution reaction. The inherent viscosities of the synthesized polymers were found to be 0.55–0.66 dL g^?1 in N,N′‐dimethylacetamide. The cardo polyimides showed excellent solubility in organic solvents, high glass transition temperatures (T_g) of 275–312 °C and moderate thermal stability with 5% weight loss temperatures (T_d5%) of 415–441 °C in nitrogen and 370–436 °C in air. The polyimide films exhibited high optical transparency with cut‐off wavelengths of 350–355 nm and moderate mechanical properties. The different properties of the polymers caused by trans and cis configurations of 1,4‐diaminocyclohexane were also investigated. It was found that with an increasing content of trans configuration of 1,4‐diaminocyclohexane in the polyimide backbone, T_g of the polyimides increased as well as T_d5%, while the solubility gradually decreased. The polyimide films had good optical transparency regardless of trans/cis configuration. © 2018 Society of Chemical Industry     

Studies of fluorine‐containing bismaleimide resins part I: Synthesis and characteristics of model compounds

A series of fluorine‐containing bismaleimide (FBMI) monomers are synthesized by a 3‐step reaction for using as the applications of low‐k materials. The synthesized FBMI monomers are characterized by the ¹H, ¹³C, ¹⁹F nuclear magnetic resonance (NMR) spectroscopy and element analysis. These FBMI monomers react with free radical initiator or self‐cure to prepare FBMI‐polymers. All the self‐curing FBMI resins have the glass transition temperatures (T_g) in the range of 128–141°C and show the 5% weight loss temperatures (T_5%) of 235–293°C in nitrogen atmosphere. The higher heat resistance of self‐curing FBMI resin relative to FBMI‐homopolymer is due to its higher crosslinking density. The FBMI resins exhibit improved dielectric properties as compared with commercial bismaleimide (BMI) resins with the dielectric constants (D_k) lower than 2.49, which is related to the low polarizability of the C? F bond and the large free volume of CF₃ groups in the polymers. Besides, the flame retardancy of all these FBMI resins could be enhanced via the introduction of Br‐atom. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Glycidyl Azide Polymer Crosslinked Through Triazoles by Click Chemistry: Curing,Mechanical and Thermal Properties

Glycidyl azide polymer (GAP) was cured through “click chemistry” by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3‐dipolar cycloaddition reaction to form 1,2,3‐triazole network. The properties of GAP‐based triazole networks are compared with the urethane cured GAP‐systems. The glass transition temperature (T_g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T_g in comparison to the GAP‐urethane system (T_g−20 °C) and the networks exhibit biphasic transitions at 61 and 88 °C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)‐based theoretical calculations implied marginal preference for 1,5‐addition over 1,4‐addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP‐triazole and the mechanism of decomposition was elucidated using pyrolysis GC‐MS studies. The higher heat of exothermic decomposition of triazole adduct (418 kJ ⋅ mol⁻¹) against that of azide (317 kJ ⋅ mol⁻¹) and better mechanical properties of the GAP‐triazole renders it a better propellant binder than the GAP‐urethane system.     

Characterization of epoxies cured with bimodal blends of polyetheramines

DGEBA was cured with bimodal blends of polyetheramines as well as with single molecular weight amines while maintaining stoichiometry. Glass transition temperatures (T_gs) and moduli were measured using dynamic mechanical analysis (DMA). Fracture properties were measured using the compact tension geometry and testing was performed at both ambient and non‐ambient temperatures, investigating toughness changes as a function of temperature. For constant amine average molecular weights, the addition of high molecular weight amines caused increased glassy moduli at a constant T ? T_g and decreased densities while broadening the glass transition without changing the fracture toughness. The fracture behavior, specifically the slip‐stick to brittle transition, was affected by the broadened transitions. T_g, breadth of T_g, and total damping were found to be proportional to the volume fraction of amine in the system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1621–1631, 2013     

Structure–property relationships in photopolymerizable polymer networks: Effect of composition on the crosslinked structure and resulting thermomechanical properties of a (meth)acrylate‐based system

Photoinitiated polymer networks were formed by copolymerization of tert‐butyl acrylate with di(ethylene glycol) dimethacrylate (DEGDMA) or poly(ethylene glycol) dimethacrylate (PEGDMA). The degree of crosslinking was systematically varied by modifying the weight fraction and molecular weight of the dimethacrylate crosslinking agent. An increase in effective crosslink density with increasing crosslinking agent concentrations was confirmed by decreasing equilibrium swelling ratios (q) and increasing rubbery moduli (E_R). Glass transition temperatures (T_g) varied from ?22 to 124°C, increasing with increasing DEGDMA content and decreasing with increasing PEGDMA content. Tensile deformation behavior (at T_g) ranged from an elastomeric‐like large‐strain response for lightly crosslinked materials to a small‐strain brittle response for highly crosslinked networks. At low crosslinking levels, the strain‐to‐failure of the network polymers decreased quickly with increasing crosslinking agent concentration. The stress at failure demonstrated a more complex relationship with crosslinking agent concentration. The effect of composition on network structure and resulting properties (q, E_R, strain‐to‐failure) decreased as the crosslinking agent concentration increased. The results reveal trade‐offs in T_g, E_R, strain‐to‐failure, and failure stress with composition and network structure, and are discussed in light of the wide range of potential applications suggested in the literature for (meth)acrylate‐based photopolymerizable polymer networks including biomaterials and shape‐memory polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Conversion–temperature–property diagram for a liquid dicyanate ester/high-Tg polycyanurate thermosetting system

The effects of conversion and temperature on the dynamic mechanical properties (at ≈ 1 Hz) of a dicyanate ester/polycyanurate thermosetting system are investigated after cure using torsional braid analysis (TBA). Extent of conversion is measured by T_g. The isothermal glassy-state modulus at measurement temperatures below the glass transition temperature of the monomer (T_g0) decreases with increasing conversion. The isothermal modulus at temperatures above T_g0 passes through a maximum due to competition between increase in the isothermal glassy-state modulus at the measurement temperature due to the vitrification process during cooling and the aforementioned decrease in the modulus with increasing conversion, which is considered to be due primarily to steric constraints in the developing network. The maximum in the isothermal modulus is associated with the boundary between the glass and glass transition regions. The experimental results are summarized in a conversion (T_g)–temperature–property diagram, the T_gTP diagram, which is a framework for understanding relationships between transitions and material properties for thermosetting systems. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of ester or cyano group substituted ring-opening polymers and their hydrogenated derivatives

Ester or cyano substituted tetracyclo [4.4.0.1^2,5.1^7,10]dodec-3-enes (1) were synthesized and their metathesis ring-opening polymerization was examined. The tungsten-based ternary catalyst system polymerized them very well. The polymers showed high glass transition temperatures (T_g) and no evidence of crystallization (e.g., the T_g of the polymer derived from 8-methyl-8-methoxycarbonyl substituted monomer (1a) was 207°C, and colorless transparent films could be casted from the solution of the polymer). The stability of these high T_g polymers were too unstable, so practical thermal molding methods could not be applied to them. The hydrogenation of these polymers with a palladium catalyst decreased T_g and greatly increased thermal stability. The physical and thermal properties of the hydrogenated polymers were thoroughly investigated. Monomer 1 was successfully copolymerized with other cyclic olefins. The resultant copolymers were hydrogenated, giving thermally stable polymers. In all cases examined in this study, a decrease of T_g by hydrogenation was about 35°C, regardless of the monomer structure. These results indicate that the main-chain mobility is the major contribution to the decrease of T_g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 367–375, 1997     

Synthesis of soluble and thermally stable polyimides from 3,5‐diamino‐N‐(4‐(8‐quinolinoxy) phenyl) aniline and various dianhydrides

Three novel polyimides (PIs) having pendent 4‐(quinolin‐8‐yloxy) aniline group were prepared by polycondensation of a new diamine with commercially available tetracarboxylic dianhydrides, such as pyromellitic dianhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bicyclo[2.2.2]‐oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride. These PIs were characterized by FTIR, ¹H NMR, and elemental analysis; they had high yields with inherent viscosities in the range of 0.4–0.5 dl g⁻¹, and exhibited excellent solubility in many organic solvents such as N,N‐dimethyl acetamide, N,N′‐dimethyl formamide, N‐methyl pyrrolidone (NMP), dimethyl sulfoxide, and pyridine. These PIs exhibited glass transition temperatures (T_g) between 250 and 325° C. Their initial decomposition temperatures (T_i) ranged between 270 and 450°C, and 10% weight loss temperature (T₁₀) up to 500°C with 68% char yield at 600°C under nitrogen atmosphere. Transparent and hard polymer films were obtained via casting from their NMP solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. I. Synthesis and characterization

The cationic copolymerization of regular soybean oil, low‐saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃·OEt₂) or related modified initiators provides viable polymers ranging from soft rubbers to hard, tough, or brittle plastics. The gelation time of the reaction varies from 1 × 10² to 2 × 10⁵ s at room temperature. The yields of bulk polymers are essentially quantitative. The amount of crosslinked polymer remaining after Soxhlet extraction ranges from 80 to 92%, depending on the stoichiometry and the type of oil used. Proton nuclear magnetic resonance spectroscopy and Soxhlet extraction data indicate that the structure of the resulting bulk polymer is a crosslinked polymer network interpenetrated with some linear or less‐crosslinked triglyceride oil–styrene–divinylbenzene copolymers, a small amount of low molecular weight free oil, and minor amounts of initiator fragments. The bulk polymers possess glass‐transition temperatures ranging from approximately 0 to 105°C, which are comparable to those of commercially available rubbery materials and conventional plastics. Thermogravimetric analysis (TGA) indicates that these copolymers are thermally stable under 200°C, with temperatures at 10% weight loss in air (T₁₀) ranging from 312 to 434°C, and temperatures at 50% weight loss in air (T₅₀) ranging from 445 to 480°C. Of the various polymeric materials, the conjugated LoSatSoy oil polymers have the highest glass‐transition temperatures (T_g) and thermal stabilities (T₁₀). The preceding properties that suggest that these soybean oil polymers may prove useful where petroleum‐based polymeric materials have found widespread utility. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 658–670, 2001     

Direct functionalization with 3,5‐substituted benzoic acids of multiwalled carbon nanotube/epoxy composites

Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (T_p) and exothermic heat of reaction (ΔH). The values of activation energy (E_a) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (f_g) decreased, resulting in dramatic increase of glass transition temperatures (T_g) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers