Tribological properties of polyesterimide and its composites

Polyesterimide (PEI) and phenol formaldehyde (PF) samples were synthesized, and composites of the two polymers, as well as composites with carbon, were prepared. Using a pinon-disc machine, the friction and wear properties of the following samples were studied in the load range of two to eight bars:

• Phenolformaldehyde vs. steel
• Phenol formaldehyde cured with hexamethylenetetramine vs. steel
• Polyesterimide vs steel
• Polyesterimide and carbon composite vs steel
• Phenol formaldehyde vs polyesterimide
• Phenol formaldehyde and polyesterimide composite vs. phenol formaldehyde
• Phenol formaldehyde and polyesterimide composite vs. steel.

The data obtained from these experiments were compared with literature data on poly(tetrafluoroethylene) and nylon, conventionally used for tribological applications. It is seen that, in terms of thermal stability, friction, and wear, PEI and PF are promising for tribological applications.     

Investigation in thermal endurance of polyesterimide used in electrical machines

The purpose of this investigation is to evaluate thermal lifetime of polyesterimide using Weibull statistics. Thermal aging was performed on twisted pair specimens of copper wire insulated by a polyesterimide layer. The study shows that breakdown voltage varies versus aging time. Its increase is allotted to a crosslinking inducing a diminution of mean‐free path of charge carriers leading thereby to a mobility decrease, whereas its decrease is attributed to the viscosity diminution expressing a weakening of molecular bonds and a mobility increase of charge carriers. Shape parameter changes in function of aging time. Its increase is ascribed to an arrangement of the molecular structure, whereas its decrease is due to an augmentation in the size of defects. The thermal endurance graph is a straight line indicating that the degradation is governed by a first‐order chemical reaction. Activation energy and temperature index were determined. The degradation is governed by the dissolution of copper into the polymer and accelerates its degradation occurring at the polyesterimide–copper interface. Oxygen can diffuse into the insulation and attack copper resulting in the formation of copper oxide. The degradation is caused by the scission of imide and ester bonds. The process is followed by a change in color and a presence of cracks. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal decomposition kinetics of thermotropic liquid crystalline polyesterimides

We investigated the thermal decomposition behavior of three groups of polyesterimides that had been synthesized from different compositions of monomers that were added in different. We characterized these polymers with thermogravimetric analysis (TGA) and calculated the apparent activation energy (E_a) associated with the thermal decomposition process by the Ozawa method. The results showed that the E_a of the polyesterimides was correlated with the length of the methylene spacer and the content of the 4,4′‐dihydroxybenzophenone monomer. The polyesterimide with four methylene spacers in the main chain had a higher E_a than that with six methylene spacers. The polyesterimide with a higher 4,4′‐dihydroxybenzophenone content provided better thermal stability. The E_a of the polyesterimides also depended on the sequence in which the monomers were added during the copolycondensation process. The E_a of these polyesterimides followed the order: p‐hydroxybenzoic acid added first > p‐hydroxybenzoic acid mixed 4,4′‐dihydroxybenzophenone adding > 4,4′‐dihydroxybenzophenone added first. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2467–2472, 2005     

N-(carboxymethyl) trimellitimide–based polyesterimides as film formers for air-drying protective coatings

N-(carboxymethyl) trimellitimide, the imidodicarboxylic acid, was prepared by the reaction between trimellitic anhydride and glycine. This was subsequently condensed in N-methyl-2-pyrrolidone with the alcoholysis products obtained from linseed oil and glycerine to get different oil length polyesterimide resins. The drying characteristics of the resins and the physicochemical properties of the clear and the iron oxide pigmented coatings were evaluated. The results indicate that these materials form a promising class of film—formers for coatings of good durability and protective properties.     

Synthesis and properties of polyesterimides and their isomers

A new type of polyesterimide has been synthesized by polycondensation of a dicarboxylic acid containing an internal imide group with ethylene glycol. The dicarboxylic acid was synthesized by reacting aminobenzoic acid with trimellitic acid anhydride in N, N-dimethylformamide solution. Three isomeric (ortho, meta, and para) polyesterimides were prepared from the respective isomer of the dicarboxylic acid. The solubility characteristics, solubility parameters, solution viscosity behavior, density, crystallinity, and thermal properties of these three isomeric polyesterimides were discussed. Some generalizations about structure–property relationship in polyesterimides were also made. It was found that while the ortho and meta isomers of the polyesterimide are amorphous, the para isomer tends to be somewhat crystalline and consequently less soluble, even in polar solvents. The thermal behavior of the meta isomer resembles closely that of the para isomer. The thermal stability of these isomers follows the order para ≥ meta > ortho.     

Accelerated crystallization of poly(L‐lactide) by physical aging

The low‐temperature physical aging of amorphous poly(L ‐lactide) (PLLA) at 25–50°C below glass transition temperature (T_g) was carried out for 90 days. The physical aging significantly increased the T_g and glass transition enthalpy, but did not cause crystallization, regardless of aging temperature. The nonisothermal crystallization of PLLA during heating was accelerated only by physical aging at 50°C. These results indicate that the structure formed by physical aging only at 50°C induced the accelerated crystallization of PLLA during heating, whereas the structure formed by physical aging at 25 and 37°C had a negligible effect on the crystallization of PLLA during heating, except when the physical aging at 37°C was continued for the period as long as 90 days. The mechanism for the accelerated crystallization of PLLA by physical aging is discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical relaxations in heat‐aged polycarbonate. Part II: Statistical analysis of low‐molecular weight data

The significance of heat‐aging effects on low‐molecular‐weight polycarbonate has been studied by performing a two‐factor Analysis of Variance (ANOVA). Although this work was primarily motivated by the large experimental scatter observed in stress relaxation results for LMW 2608 (part I), the effect of heat‐aging on the characteristics of secondary transitions (γ and β₁) generated by dynamic testing was also investigated. Both types of tests were performed using a dynamic mechanical analyzer. The statistical analysis verified an earlier suggestion that both the secondary transitions were insensitive to heat‐aging. In the quasi‐static stress relaxation tests, the curve‐fitted KWW parameters (τ, E_o′ β′) were evaluated using ANOVA for increasing heat‐aging time and test temperature. Two other statistical techniques were also applied to test repeatability—the power of each aging time/test temperature combination and the number of observations needed to achieve 90% repeatability. In conclusion, both τ and β′ could describe the self‐retarding nature of volume recovery although the repeatability of β′ was substantially higher. However, the unrelaxed modulus, E_o, was found to be an unreliable indicator of whether heat‐treatment had caused changes in the intrinsic structure. Overall, the study showed that the repeatability of the stress relaxation test results is generally very poor for the confidence levels tested.     

Electrical aging of polyurethane under ac voltage

The electrical aging of polyurethane under ac voltage has been investigated using Weibull statistical analysis. It is shown that the time to breakdown characteristic (V-t) of this polymer includes three zones corresponding, respectively, to the youth defects, the statistical dispersion of the intrinsic defects, and the real aging of the polymer. The variation of slope of the V-t curve is related to the change of the degradation mechanism. This degradation is governed by the action of partial discharges according to three stages: (1) the appearance of very fast discharges within the cavities; (2) the initiation of discharges resulting of a very thin layer of oxidation products; and (3) the formation of crystals having small dimensions leading to degradation by electrical tree. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Upgrading of acrylonitrile–butadiene copolymer properties using natural rubber–graft–N‐(4‐aminodiphenylether) acrylamide

The grafting of ADPEA onto natural rubber was executed with UV radiation. Benzoyl peroxide was used to initiate the free‐radical grafting copolymerization. Natural rubber‐graft‐N‐(4‐aminodiphenylether) acrylamide (NR‐g‐ADPEA) was characterized with an IR technique. The ultrasonic velocities of both longitudinal and shear waves were measured in thermoplastic discs of NBR vulcanizates as a function of aging time. Ultrasonic velocity measurements were taken at 2 MHz ultrasonic frequency using the pulse echo method. We studied the effect of aging on the mechanical properties and the swelling and extraction phenomena for acrylonitrile–butadiene copolymer (NBR) vulcanizates, which contained the prepared NR‐g‐ADPEA and a commercial antioxidant, N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine. The prepared antioxidant enhanced both the mechanical properties of the NBR vulcanizates and the permanence of the ingredients in these vulcanizates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrical insulation properties of silicone rubber under accelerated corona and thermal aging

A contactless method based on energy shift of high-energy cut-off of the x-ray bremsstrahlung, the so-called Duane Hunt Limit and a conventional low voltage electrical technique (three-probes technique) is applied on thermal and corona aged silicone rubber (SiR) to measure, respectively, the surface potential, V_s, and the surface resistivity, ρ_s. The effect of aging on these quantities, representing the dielectric properties, is studied. The results are highly reproducible and highlight a good correlation between V_s and ρ_s. It was observed that thermal aging combined with electrical aging deteriorates more the electrical properties of the polymer than thermal aging alone. Explanations for electrical characteristics (V_s, ρ_s) change with aging are supported by attenuated total reflection Fourier transform infrared spectroscopy spectra analysis and a chemical mechanism of aging in three steps (i.e., oxidation-polycondensation, degradation, and thermal cracking). The surface degradation of the polymer is revealed by images of surface morphology obtained by using scanning electron microscopy (SEM). Roughness is greater for combined thermal and corona aging mode compared to thermal aging alone. In addition, the surface degradation of SiR polymer is confirmed by the loss of its hydrophobicity.     

Physical aging deep in the glassy state of a fully cured polyimide

Physical aging of a fully cured polyimide/glass fiber specimen has been investigated deep in the glassy state using a freely oscillating torsion pendulum (TBA). A single specimen, the physical aging effects of which could be erased by heating to above T_g = 304°C (0.8 Hz), could be used for all experiments. Data were obtained during isothermal aging at different aging temperatures, T_α, (from 10°C to T_g) and during subsequent temperature scans (T_α to 5 to 315°C). The aging rate depended upon the value of T_α relative to both T_g and the β-relaxation temperature, T_β = 139°C (1.3 Hz). Changes in thermomechanical behavior due to aging were localized about T_α. This suggests that only an intermediate portion of the relaxation spectrum participates in, and is affected by, isothermal physical aging. It follows, and is observed, that the intensity of the β-relaxation mechanical loss peak is perturbed most significantly by aging at T_α near T_β. The effect of isothermal aging deep in the glassy state could be essentially eliminated by heating to below T_g. © 1992 John Wiley & Sons, Inc.     

Thermal transition behaviors in a liquid crystalline polyesterimide

The crystallization and melting behaviors of the polyesterimide, derived from N,N′-hexane-1,6-diylbis(trimellitimides), 4,4′-dihydroxybenzophenone and p-hydroxybenzoic acid, were investigated by using polarized light microscopy (PLM), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). The nematic texture of the polyesterimide was observed on raising temperature to 265 °C, and the nematic phase was found to convert to isotropic melt beginning from about 300 °C, the ordered nematic micro-domains still surviving after 320 °C. Isothermal crystallization of the samples was performed at 180 °C after heating samples at various temperatures in the range of 265-360 °C, and a completed crystallization peak can appear on DSC curves up to the heating temperature of 360 °C in the presence of the nematic phase and the ordered nematic micro-domains. Non-isothermal crystallization of the samples at different cooling rate was carried out, and the melting of the resulting crystals exhibits double endotherms. It is indicated that a fast crystallization in the nematic phase forms relatively more ordered crystals, which melt at higher temperature, and a slow crystallization in the isotropic phase or in the biphasic melt produces poor crystals, which melt at lower temperature. The crystallized polyesterimide was annealed, which has a minor effect on the high-melting peak but leads to a continual shifting of the low-melting peak to higher temperature with increasing annealing temperature or annealing time. WAXD patterns indicated that the structural transform was not found during annealing process.     

Isothermal physical aging of a fully cured epoxy—amine thermosetting system

The rate and effects of isothermal physical aging of a fully cured epoxy—amine/glass fiber composite specimen were studied for a wide range of isothermal aging temperatures (−180 to 200°C) using a freely oscillating torsion pendulum technique: torsional braid analysis (TBA). As assigned from the maxima in the mechanical loss vs. temperature, the glass transition temperature, T_g, was 182°C (0.9 Hz), and the principal glassy-state secondary transition temperature, T_β, was ≈ −30°C (1.9 Hz). Plots of the increase in the isothermal modulus and of the decrease in the isothermal mechanical loss were linear vs. log aging time; their slopes provided aging rates. It was found that the isothermal aging rate varies with isothermal aging temperature (T_a) and that there are two maxima in the aging rate vs. T_a. A correlation presumably exists between the two maxima in the aging rate and the two transitions. This is not surprising since mechanical loss maxima (i.e., transitions) and aging rate maxima both correspond to specific, localized, and restricted submolecular motions. Effects after isothermal physical aging were investigated vs. temperature in terms of change of modulus of the specimen. The effect of isothermal aging existed primarily in a narrow temperature region localized about T_a. The majority of the isothermal aging effect can be eliminated by heating to temperatures above T_a, but below T_g. Theoretical and practical implications of this observation are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 55–67, 1997     

Hydroxytelechelic hydrocarbon copolymers with high aging resistance for elastomeric materials

Dihydroxytelechelic copolyalkenamers were prepared via metathetical polymerization of cyclic olefins (cyclooctadiene, cyclooctene and cyclododecene) in presence of first generation Grubbs catalyst and butene diacetate as functionalizing chain transfer agent in order to study their aging resistance. The influence of compositions and molar masses of the copolyalkenamers were investigated in terms of thermo‐mechanical properties. Increasing chains length or the proportion of polycyclooctadiene allow to get non‐cristalline polymers. Low T_g materials (between ?78°C and ?108°C) were prepared. The resistance towards oxidation of the different copolyalkenamers was carried out using a viscosity measurement method. A critical time, corresponding to a brutal increase of the apparent viscosity, was related to degradation of the polymers and was shown to be dependent on the Csp² proportion in the structure. The absence of vinylic units and the decrease of the double bonds content within the copolymers were proved to enhance the stability of the copolyalkenamers towards aging resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Exploration of alternative models for the aging of fouling deposits

The effect of fouling in heat‐transfer devices (HTDs) is complicated by aging of the fouling deposits. Aging is, like deposition, often sensitive to temperature, so that heat transfer, deposition, and aging are coupled phenomena. Ishiyama et al. (AIChE J. 2010;56:531–545) presented a distributed model of the aging of deposits formed by chemical reaction fouling and illustrated its effect on thermal and hydraulic performance of a HTD operating in the turbulent flow regime. Two‐layer models, simpler than the distributed model, are explored. The deposit is considered to consist of two layers, fresh and aged; this simple picture is shown to be sufficient to interpret thermal and hydraulic aspects of deposit aging when HTDs are operated at constant heat flux (as reflecting laboratory experiments) but not in cases where the constant wall temperature approximation is more realistic. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Effect of hot air aging on the properties of ethylene‐vinyl acetate copolymer and ethylene‐acrylic acid copolymer blends

The aim of this investigation is to evaluate the effect of hot air aging on properties of ethylene‐vinyl acetate copolymer (EVA, 14 wt % vinyl acetate units), ethylene‐acrylic acid copolymer (EAA, 8 wt % acrylic acid units), and their blends. Attenuated total reflection‐Fourier transform infrared spectroscopy, differential scanning calorimeter (DSC), wide angle X‐ray diffraction, and mechanical tests are employed to investigate the changes of copolymer blends' structures and properties. Increase of carbonyl index derived from ATR measurements with aging time suggests the incorporation of oxygen into the polymeric chain. By DSC measurements, the enthalpy at low temperature endothermic peak (T_m2) of EAA becomes less and disappears after 8 weeks aging, but enthalpy at T_m2 of EVA is not influenced by the hot air aging and remains stable despite of the aging time. For various proportions of EAA and EVA blends, enthalpy at T_m2 decreases as the EAA proportion increases when aging time is 8 weeks; after several weeks of hot air aging, the various blends appear a same new peak just over the aging temperature 70°C which is due to the completion of crystals which are not of thermodynamic equilibrium state. Mechanical tests show that increase of crystallinity and hot air aging deterioration both have influence on the hardness, tensile strength, and elongation at break. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Physical aging in the glassy state of a thermosetting system vs. extent of cure

The physical aging behavior of a high-T_g amine/epoxy thermosetting system has been investigated vs. change of chemical structure induced by cure and vs. aging temperature (T_a) using the Torsional Braid Analysis (TBA) technique. The chemical structure was changed systematically from monomer to highly crosslinked polymer by curing in the equilibrilium state (T > T_g). The aging temperatures ranged from just below the glass transition temperature to deep in the glassy state (T_a > T_g). In the absence of chemical reaction, the physical aging rate at a given temperature, T_a, passes through a minimum with increasing chemical conversion (i.e., change of chemical structure). Analysis of this behavior is simplified by using T_g as an index of measurement of extent of cure. There is a superposition principle for normalizing the physical aging behavior of the thermosetting glasses, which involves a shift of T_g–T_a and a shift of C(T_a) (a function of aging temperature), regardless of chemical structure. Analysis reveals that: (1) this behavior is the consequence of the T_g and T_β transitions, (2) the segmental mobility (1/τ) is a function of the deviation from equilibrium (as measured by T_g–T_g and the aging time), (3) the segmental mobility, which is involved in the physical aging process in the glassy state, is insensitive to the extreme changes of chemical structure (from monomer, to sol/gel polymer, and to highly crosslinked polymer), and (4) physical aging deep in the glassy state affects both segmental mobility and cohesive energy density. © 1993 John Wiley & Sons, Inc.     

Erasure below glass‐transition temperature of effect of isothermal physical aging in fully cured epoxy/amine thermosetting system

The erasure below the glass‐transition temperature (T_g) of the effect of isothermal physical aging (at aging temperature T_a) in a fully cured epoxy/amine thermosetting system is investigated using the torsional braid analysis (TBA) dynamic mechanical analysis technique and the differential scanning calorimetry (DSC) technique. From the TBA temperature scans, the intensity of the localized perturbation of the moduli in the vicinity of the T_a (90°C), due to isothermal physical aging, is decreased by heating to below the T_g (T_g∞ = 177°C), indicating that the physical aging effect can be eliminated by heating to below the T_g. The isothermal aging effect in the vicinity of the T_a is almost completely eliminated by heating to 50°C above the T_a (i.e., 140°C); however, a competing aging effect occurs above T_a at higher temperatures during the heating. Erasure below T_g of the isothermal physical aging effect is inferred from DSC experiments from the diminished relaxation enthalpy in the vicinity of the T_g, which is measured from the difference in areas between the aged (T_a = 150°C) and deaged thermograms. A comparison of the TBA and DSC results is made. Implications on the heterogeneous nature of the amorphous glassy state of polymers are discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 396–404, 2001     

Effects of stress and vapor exposure before and during aging on enthalpy relaxation of poly(vinyl chloride)

Enthalpy relaxations in glassy poly(vinyl chloride) following varied pre-aging treatments and under varied aging conditions have been compared through observations of sub-T_g endothermal DSC (differential scanning calorimetry) aging peaks. The extent of enthalpy relaxation for a fixed time and temperature of aging is progressively enhanced by the imposition and release of increasing mechanical stress before aging. The same effect is produced by sorption and desorption of increasing amounts of CO₂ or CH₃Cl vapor before aging. In contrast, the continued application of mechanical stress, or the presence of vapor, during the aging period suppresses enthalpy relaxation. The extent of suppression increases with increasing vapor pressure and solubility or increasing stress. These effects are interpreted as consequences of an increase in the enthalpy of the polymer under mechanical or sorptive stress and an enthalpy relaxation following the release of this stress. In addition to these effects on the DSC endotherm, a pronounced exotherm between the aging peak and T_g is observed for samples which have undergone shear yielding or orientation either before or during aging. This exotherm may be the result of release of stored strain energy during the DSC scan.     

Physical aging of high-performance thermoplastics: Enthalpy relaxation in PEK-C and PES-C

The developments of physical aging in phenolphthalein poly(aryl-ether-ketone) (PEK-C) and poly(aryl-ether-sulfone) (PES-C) with time at two aging temperatures up to 20 K below their respective glass transition temperatures (T_g = 495 and 520 K) have been studied using differential scanning calorimetry (DSC). Substantial relaxation within the aging course of several hours were observed by detecting (T_g) decreasing during physical aging process at the two aging temperatures. The relaxation processes of both polymers are extremely nonlinear and self-retarding. The time dependencies of their enthalpies during the initial stages of annealing were approximately modeled using the Narayanaswamy-Tool model. The structure relaxation parameters obtained from this fitting were used to predict the possibility of physical aging occurring at their respective using temperatures. © 1995 John Wiley & Sons, Inc.