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The physical aging properties of amorphous thermoplastics having various terminal groups were investigated with creep recovery and linear dilatometry. The structure of the chain end groups affected physical aging at lower molecular weights; however, above the critical molecular weight for entanglements the end-group effect on aging diminished. Experimental densities and glass-transition temperatures were also end-group dependent. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2850–2860, 2003

High molecular weight, soluble, amorphous, partially aliphatic polyimides were successfully synthesized using an ester acid high-temperature solution imidization route, which allows one to control desired glass-transition (T g ) and processing temperatures. This method involves the prereaction of aromatic dianhydrides with ethanol and a tertiary amine catalyst to form ester acids, followed by the addition of diamines. Subsequent thermal reaction forms fully cyclized polyimides. This reaction pathway eliminates the need for anhydrous solvents and overcomes the problem of salt formation commonly observed for nucleophilic, more-basic aliphatic amines when utilizing the traditional polyamic acid synthesis route. The molar ratio of aromatic-to-aliphatic diamines was varied to generate a series of copolyimides with the chosen dianhydride and tailor the physical properties for specific adhesive applications. This series of copolyimides was characterized by their molecular weight, T g , thermal stability, coefficient of thermal expansion, refractive index, and dielectric constant. Structure-property relationships were established. The γ and β sub-T g viscoelastic properties were researched to understand their molecular origins.

This study focuses on bisphenol A polycarbonate and tracks changes in the properties of this material as a function of the degree of degradation, τ, induced by a hostile environment. Among many possible environmental effects, we have limited this investigation to those associated with elevated temperature, although the methodology is general. This τ parameter is a product of the kinetic rate constant, k, found from isothermal kinetics, and the time of degradation, t. The elucidation of τ has been linked to the measurement of the molecular weight distribution, which, in turn, can be related to various properties to yield valuable predictive relationships. Only the thermal history of the polymer and its initial properties are required for the model. This technique is not limited to a specific polymer or even to thermal degradation. As long as the kinetics of the process can be mathematically modeled, this approach should apply to a host of other situations, providing property prediction simply from knowledge of the material history. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 794–801, 2002

A general scheme is presented in the first part of this series in which degradation-induced changes in a polymer that are produced by exposure to an aggressive environment are linked to measurable kinetic parameters and molecular weight distribution variations. Although general in nature for all polymers and environments, the data were collected on bisphenol A polycarbonate that was degraded by elevated temperatures. A parameter, τ, the product of a kinetic rate constant, k, and the environmental exposure time, provided a metric that was suitable for superposition methods to reduce the data. τ was directly related to the molecular weight distribution shifting during environmentally induced changes. This article extends the methodology to structure–property correlations such as the relationship of the glass-transition temperature, rheology, and the tensile strength of polycarbonate after the environmental treatment. Again, in a universal fashion, the τ value (the degree of degradation) was sufficient to model the observed physical property changes with the amount of exposure to the hostile environment. As long as the kinetics of the process of change are amenable to a mathematical model and a quantitative measure of the change in a fundamental polymer parameter is available, this methodology should be applicable to any polymer in any environment. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 802–812, 2002

We present a continuing investigation of epoxies based on diglycidyl ether of bisphenol A cured with 2-ethyl-4-methylimidazole in the presence of the nonionic surfactant Triton X-100. Interest in this epoxy system is due partially to its potential application as a waterborne replacement for solvent-cast epoxies in E-glass-laminated printed circuit boards. The surfactant additive could potentially alter the interfacial properties and durability of composite materials. Previous studies revealed that the viscoelastic behavior of the cured epoxy is altered when it serves as the matrix in a glass-fiber-reinforced composite. The additional constraining and coupling of the E-glass fibers to the segmental motion of the epoxy matrix results in an apparent increased level of viscoelastic cooperativity. Current research has determined that the cooperativity of an epoxy/E-glass composite is also sensitive to the surface chemistry of the glass fibers. Model epoxy/E-glass composites were constructed in which the glass was pretreated with either 3-aminopropyltriethoxysilane or 3-glycidoxypropyltrimethoxysilane coupling agents. Dynamic mechanical analysis was then used to create master curves of the storage modulus in the frequency domain. The frequency response of the master curves and resulting cooperativity plots clearly varied with the surface pretreatment of the glass fibers. The surfactant had surprisingly little effect in the observed trends in the cooperativity of the composites. However, the changes in cooperativity due to the surface pretreatment of the glass were lessened when the samples were prepared from waterborne emulsions. Moisture-uptake experiments were also performed on epoxy samples that were filled with spherical glass beads as well as multi-ply laminated composites. No increases in the diffusion constant could be attributed to the surfactant. However, the surfactant did enhance the final equilibrium moisture-uptake levels. These equilibrium moisture-uptake levels were also sensitive to the surface pretreatment of the E-glass.

Anisotropy in a polyimide film was investigated in a quantitative manner by a nonlinear regression of the thermal shrinkage data obtained from thermomechanical analysis. The thermally induced shrinkage of this pyromellitic dianhydride–oxydianiline polyimide film at 573 K was directionally anisotropic in the film plane by as much as about 0.4%. The direction of maximum thermal shrinkage was inclined by about π/6 rad from the machine direction of the film. The thermal shrinkage behavior of the polyimide films in the vicinity of the glass-transition temperature (Tg) showed an unusual anisotropic response. On the basis of a correlation between the anisotropy in the thermal shrinkage of the films and the molecular orientation of the polyimide, this characteristic thermal shrinkage behavior around Tg is suggested to be due to a recovery of the free volume lost by a physical aging process. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3222–3229, 2000

Nonreactive bisphenol A-based poly(arylene ether triphenyl phosphine oxide/diphenyl sulfone) statistical copolymers and a poly(arylene ether triphenyl phosphine oxide) homopolymer, each having a number-average molecular weight of about 20 kg/mol, were synthesized and solution-blended with a commercial dimethacrylate vinyl ester resin. Free-radical cured systems produced morphologies that were a function of both the amount of phosphonyl groups and the weight percentage of the copolymers. For example, highly hydrogen-bonded poly(arylene ether phenyl phosphine oxide) homopolymer/vinyl ester resin mixtures were homogeneous in all proportions both before and after the formation of networks. Copolymers containing low amounts (≤30 mol %) of the phosphonyl groups displayed phase separation either before or during cure. The phase-separated cured materials generally had phase-inverted morphologies, such as a continuous thermoplastic copolymer phase and a particulate, discontinuous vinyl ester network phase, except for systems containing a very low copolymer content. The resin modified with a copolymer containing 30 mol % phosphine oxide comonomer showed improved fracture toughness, suggesting the importance of both phase separation and good adhesion between the thermoplastic polymer and the crosslinked vinyl ester filler phase. The results suggested that the copolymers with high amounts of phosphine oxide should be good candidates for interphase sizing materials between a vinyl ester matrix and high-modulus carbon fibers for advanced composite systems. Copolymers with low amounts of phosphonyl groups can produce tough, vinyl ester-reinforced plastics. The char yield increases with the concentration of bisphenol A poly(arylene ether phosphine oxide) content, suggesting enhanced fire resistance. The incorporation of thermoplastic copolymers sustains a high glass-transition temperature but does not significantly affect the thermal degradation onset temperature.

We have investigated epoxies based on the diglycidyl ether of bisphenol A (DGEBA) cured with 2-ethyl-4-methylimidazole (EMI-24) in the presence of the nonionic surfactant Triton X-100. A goal was to determine if the viscoelastic properties of the epoxy–surfactant system differed when prepared in bulk form, as opposed to being cast as a thin film on the surface of E-glass cloth. Such a combination of materials has generated great interest for potential use in the construction of laminated circuit boards. Using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and atomic force microscopy (AFM), it was determined that the surfactant acts as a plasticizer and is miscible with the epoxy system in concentrations up to 15% by weight. The glass transition temperature (Tg) depression of the epoxy due to the surfactant was accurately described by the Fox equation. DMA master curves were constructed in the frequency domain. The temperature dependence of the shift factors was used to determine the fragility of each of the samples studied. It was found that the fragility (cooperativity) of the epoxy decreased as the concentration of surfactant increased, presumably due to a reduction of intermolecular constraints. The fragility of the combined epoxy–surfactant system increased when cast on the surface of the E-glass cloth. Results for our model epoxy–surfactant resin were in excellent agreement with those obtained using a commercially available aqueous waterborne epoxy resin. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2781–2792, 1998

Soluble, fully cyclized m-amino phenyl acetylene terminated polyimides based on several anhydride/diamine monomers were prepared in N-methylpyrrolidine (NMP) and cyclized by solution imidization to controlled molecular weight. The polyimides and a polyamic acid precursor were successfully analyzed by size exclusion chromatography (SEC) utilizing online parallel coupled refractive index and differential viscometer detectors. The calculated Mnvalues were varied from 3,000 to 20,000 daltons. N-methylpyrrolidone (NMP), tetrahydrofuran (THF), and chloroform served as mobile phases for the cross-linked polystyrene gel packings. Normal retention behavior of the polyimides was observed in chloroform, THF, and NMP containing LiBr, or in NMP stirred over P2O5 before use. Values of Mark-Houwink-Sakurada exponents for narrow distribution linear polystyrene indicate that pure NMP and NMP with 0.06 M LiBr are good solvents for polystyrene standards at 60°C. In contrast, SEC behavior of polyimides in pure NMP leads to splitting of the peaks with the major portion observed to pass through the columns at the exclusion limit. In contrast to strong polymeric chain expansion of the polyamic acid in dilute solution, presumably due to a polyelectrolyte effect, no increase of intrinsic viscosity of polyimide samples in pure NMP was observed. This exclusion effect of polyimides analyzed in NMP is discussed in terms of possible ion-exclusion from pores of the stationary phase. Differences in polystyrene calibration in NMP with or without additives and the temperature dependence of calibration curves in these mobile phases is discussed as well. ©1995 John Wiley & Sons, Inc.

Six different soluble high-performance aromatic polyimides, each prepared by solution imidization to three controlled average molecular weights, were analyzed by size exclusion chromatography (SEC) using on-line parallel coupled refractometric and viscometric detectors. N-methylpyrrolidone (NMP) with 0.06 M LiBr and NMP stirred over P2O5 were used as mobile phase for four of the polyimides; NMP with 0.06 M LiBr and NMP stirred over P2O5 were used as mobile phases for four of the polyimides; NMP with 0.06 M LiBr tetrahydrofuran (THF) and chloroform served as mobile phases for the other two polyimides. For all the samples the stationary phase in the SEC columns was cross-linked polystyrene beads. Molecular weight averages of the polyimides were calculated using universal SEC calibration with polystyrene standards in each solvent. The agreement of the calculated molecular weight averages in the different solvents confirms that the universal SEC calibrations are valid for these semiflexible polymers. There was good agreement with weightaverage molecular weights obtained by low-angle laser light scattering (LALLS) performed in pure NMP. Intrinsic viscosity and molecular weight data for a series of nine samples of one polyimide covering a Mw = 20,000–70,000 g mol–1 interval were treated to obtain Mark-Houwink-Sakurada constants. Unperturbed chain dimensions of this polyimide were obtained by application of the Stockmayer-Fixman extrapolation procedure to these data. ©1995 John Wiley & Sons, Inc.

In a previous study, a mechanosorptive phenomenon in poly(p-phenylene terephthalamide) fibers was reported. In this article, the mechanosorptive creep mechanism of aramid fibers and the temperature and stress influences on the mechanosorptive creep behavior of aramid fibers are addressed. Test results indicate that logarithmic creep rates and the mechanosorptive effects increase with temperature. The creep activation energies of the fibers tested are: 20 kJ/mole for the cyclic moisture condition, 4.4 kJ/mole for a high equilibrium moisture condition (RH = 95%), and 7.8 kJ/mole for a low equilibrium moisture condition (RH = 5%). Increase in stress may increase the logarithmic creep rates but may reduce the mechanosorptive effect. Aramid fibers contain hydrogen bonds between rodlike crystallites oriented at small angles relative to the fiber axis. Transient moisture conditions may cause slippage of hydrogen bonded elements and result in accelerated crystallite rotations due to breakage of hydrogen bonds, thus causing increases in logarithmic creep rate. The obtained activation energies and the reduction in fiber elastic compliance due to creep deformation support the proposed mechanisms. © 1992 John Wiley & Sons, Inc.

The phase behavior of narrow molecular weight distribution samples of polystyrene and polyisoprene in the presence of toluene was investigated by means of gel permeation chromatography. Equilibrium phase diagrams, tie lines, and critical points for a number of partially miscible polystyrene-polyisoprene-toluene systems were generated at 15 and 30°C and 1 atm pressure. The data were combined with previously reported results at 45°C. Using the experimentally determined phase compositions along with literature values of the polymer–solvent interaction parameters, the polymer–polymer interaction parameters were evaluated using the Flory–Huggins theory. The influence of temperature, polymer molecular weight, and polymer–solvant interaction parameters on the size, shape, and location of the equilibrium phase curve, the location of the critical point, and the polymer–polymer interaction parameter was studied.

High-temperature polyimide films with metallic gold surfaces can be fabricated by the incorporation of a soluble metal salt into a solution of polyamic acid. Thermal treatment of these solutions produces the polyimide, decomposes the metal salt to metallic gold, and promotes the formation and growth of the metallized surface. What appeared to be a continuous metallic surface was actually composed of large gold aggregates. It is suspected that the formation of colloidal gold during the initial thermal treatment provides precursors to the large metal aggregates. Thermal treatment has been shown to influence the size and distribution of the aggregates. The shape of the aggregates suggests that diffusion-limited aggregation may be responsible for the unique shape of some of the gold aggregates.

Equilibrium phase diagrams of narrow molecular weight distribution samples of polystyrene and polyisoprene in the presence of toluene at 45°C and 1 atm pressure were established by means of gel permeation chromatography. The polymer-polymer interaction parameter was evaluated on the basis of the Flory-Huggins approach. The influence of polymer molecular weight and polymer-solvent interaction parameters on (i) the shape and location of the binodal curve, (ii) the location of the critical point, and (iii) the polymer-polymer interaction parameter was investigated.