Polymer Engineering and Science

A series of acetylene-terminated phenylquinoxaline (ATPQ) oligomers of various molecular weights were prepared and subsequently chain extended by the thermally induced reaction of the ethynyl groups. The processability and thermal properties of these oligomers and their cured resins were compared with that of a relatively high molecular weight linear polyphenylquinoxaline (PPQ) with the same chemical backbone. The ATPQ oligomers exhibited significantly better processability than the linear PPQ but the PPQ displayed substantially better thermooxidative stability. Adhesive (Ti/Ti) and composite (graphite filament reinforcement) work was performed to evaluate the potential of these materials for structural applications. The PPQ exhibited better retention of adhesive and laminate properties than the ATPQ resins at 260 C after aging for 500 hr at 260 C in circulating air.

A torsional pendulum which operates throughout the temperature range — 180° ⇄ +650°C, and permits the examination of specimens which conform to ASTM standard D2236 is reported. The same apparatus is used for torsional braid analyses for which a composite specimen is prepared by impregnating a multifilament glass braid with a solution of polymer and thermally removing the solvent. A linear-with-angle no-drag optical transducer which employs the linear transmission region of a pair of polarizers is described. The apparatus has been used for examining thermo-hysteresis effects in polymers. Hysteresis can arise in polymers from physical time-dependent phenomena such as crystallization ⇄ fusion, dry atmosphere ⇄ water vapor, annealing ⇄ cracking, and from chemical reactions. Thermally-induced chemical reactions can be regulated so as to freeze out preferentially longer range relaxations, thereby extending the glassy state behavior to higher temperatures. A comparison of the thermomechanical behavior of a commercially available polyimide film and of a polyimideforming varnish is reported using torsional pendulum and torsional braid analyses.

A study was made on the stress relaxation behavior at 25 C of poly(methyl methacrylate) in uniaxial tension as a function of physical aging at both room temperature and 60 C. Test specimens were compression molded at 165 C, then quenched to room temperature and allowed to age for up to 30 days prior to testing. Stress relaxation curves measured after different aging times could be superposed to a single master curve for each aging temperature. Superposition was achieved by applying vertical and horizontal shifts. Hence, the shape of the response curves was not changed by aging. This is in accordance with observations made by Struik for tensile creep curves. Volume changes as a function of physical aging were also determined. Simple exponential relationships were observed between volume and both horizontal and vertical shifts. The horizontal shift implies a shift in the effective time scale caused by a change in free volume. The vertical shifts could be correlated with changes in Young's modulus caused by a change in density. For the range of aging studied, the response time scale varied over nearly two decades of log-time. For the same conditions modulus varied by 30 percent.

Fluid absorption studies have been made for a polyetherimide thermoplastic film and a unidirectional composite of the thermoplastic with graphite fibers immersed in water. JP4 jet fuel, ethylene glycol, and hydraulic fluid. The changes in the weight, thickness, and tensile properties were measured for the film. The changes in the flexural properties of the composite were measured for specimens whose fiber orientation was transverse to their length. Only the hydraulic fluid, which caused an erosion or dissolving of the resin at the specimen surface, affected the film's properties. Both the water and the hydraulic fluid affected the flexural properties of the composite, due to capillary absorption along the fiber-resin interface.

Pyrolysis in vacuum of gamma-irradiated polytrifluoroethylene indicates increased rates of volatilization with increased dosage. At the higher radiation doses, the rate curves no longer show a maximum but resemble those previously obtained with branched polyethylenes. Studies of swelling with acetone indicate crosslinking increases with radiation dose. It is estimated that for each chain fracture caused by radiation there are approximately seven crosslinks formed. However, in addition to the crosslinks a branched structure is also being produced as evidenced by the character of the thermal degradation rate curves. Alkali treatment of the polymer sensitizes it towards dehydrofluorination and double bond formation. Subsequent rate and pyrolysis studies showed the formation of very stable residues, indicating a relatively greater thermal stability of the main chain.

The experiments described were aimed at studying systematically the effect of silyl linkages on the thermogravimetric and thermomechanical properties of aromatic polyamides. Specifically, 18 aromatic silicon-containing polyamides were synthesized via interfacial polymerization of six silicon-containing diacid chlorides with 3,3-prime-diaminodiphenylmethane, 3,3-prime-diaminobenzophenone, and 1-(3-prime-aminobenzyl)-4-(3-double prime-aminobenzoyl)benzene. All polyamides were soluble in m-cresol and N,N-dimethylacetamide, and had glass transition temperatures between 178 and 254 C. Thermogravimetric analysis conducted in static air on film specimens showed 5 and 10 percent weight losses between 331 and 400 C and 354 and 440 C, respectively. The potential gain in processability engendered by incorporation of silane substituents was offset in most cases by substantial losses in thermo-oxidative stability.

Finite element analyses were performed to investigate theoretically the effects of in-plane and out-of plane eccentricities, bending or twisting, and thickness nonuniformity on the axial stress and strain variations across the width of off-axis specimens. The results are compared with measured data and are also used to access the effects of these eccentricities on the fracture stress of off-axis fiber composites. Guidelines for detecting and minimizing the presence of eccentricities are described.

Synthetic binders are special paving materials manufactured by mixing polymers, resins and oils. These materials may have improved mechanical properties as compared to the traditional modified bitumen. This work is part of a comprehensive study on the design of synthetic binders with selected mechanical properties. In this sense, upgraded mechanical properties of the final synthetic binder can be attained by understanding and correlating the mechanical properties of its individual constituents (i.e. polymer) in the dispersing medium (i.e. oil) as a function of composition and temperature. With this aim, this work deals with the thermo-mechanical properties of recycled polymer/oil blends over a wide range of temperature and composition. Recycled polymer/oil blends are thermo-rheologically complex materials. They show a predominantly gel-like behaviour at low and intermediates temperatures, a range in which the oil seems to act as a lubricant between the polymeric chains. Blend complex viscosities can be predicted using Lecyar's mixing rule.

Plasma-polymerized tetrafluoroethylene (PPTFE) coated potassium bromide IR window are shown to possess better resistance to moisture than either ethylene or chlorotrifluoroethylene. The PPTFE-coated windows tolerated an upper limit relative humidity of about 80% at 297 K, without visible damage to either window or coating, over a period of 24 hours. Elemental analysis of the bulk, and photoelectron spectroscopy of the coating surface, showed that PPTFE coatings deposited downstream of the internal plasma reactor electrodes contained less atmospheric oxygen than coatings deposited between the electrodes; perhaps accounting for the improved moisture resistance.

Composites comprising Poly(Methyl Methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) via melt mixing followed by hot pressing were fabricated. These were characterized using X-ray diffraction (XRD), thermo gravimetric (TGA), scanning electron microscopy (SEM) and Impedance analyser for their structural, morphology and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. The composite, with 38 Vol % of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low frequency relaxation is attributed to the space charge polarization MWS effect. Theoretical models were employed to rationalise the dielectric behaviour of these composites. At higher temperatures, the relaxation peak shifts to higher frequencies, due to the merging of both {beta} and {alpha} relaxations into a single dielectric dispersion peak. The AC conductivity in the high frequency region was attributed to the electronic polarization

The development of silicon carbide-silicon nitride fibers (SiC-Si3N4) by the pyrolysis of polycarbosilazane precursors is reviewed. Precursor resin, which was prepared by heating tris(N-methylamino)methylsilane or tris(N-methylamino)phenylsilane to about 520 C, was drawn into fibers from the melt and then made unmeltable by humidity conditioning at 100 C and 95 percent relative humidity. The humidity treated precursor fibers were pyrolyzed to ceramic fibers with good mechanical properties and electrical resistivity. For example, SiC-Si3N4 fibers derived from tris(N-methylamino)methylsilane had a tensile rupture modulus of 29 million psi and electrical resistivity of 6.9 x ten to the 8th power omega-cm, which is ten to the twelfth power times greater than that obtained for graphite fibers.

Some properties and applications of a pitch carbon microsphere composite are described. The small hollow microspheres are made from the pitch which is usually a wasted by-product of petroleum refining. In contrast to high density composites or syntactic foams in which microspheres are inclusions within a continuous matrix, this composite is an aggregate of microspheres bonded together by a small amount of thermosetting polymer which does not form a continuous matrix. The result is a composite with low density and thermal expansion, modest strength and rigidity, and high porosity and carbon content. Mechanical, thermal, and sorption properties have been measured. Applications of the composite include honeycomb filler for high temperature or ionizing radiation fields and a wicking absorber for solar-powered stills.

Copoly(carbonate imides) with varying amounts of carbonate in the backbone were prepared by reacting 4,4-prime-diaminodiphenyl carbonate and 4,4-prime diaminodiphenyl ether with benzophenonetetracarboxylic acid dianhydride in dimethylacetamide at room temeprature. Homopolymers of the two diamines as well as of 3,4-prime- and 3,3-prime-diaminodiphenyl carbonate were prepared in a similar procedure and their properties compared with those of the copolymers.

This paper develops a damage model for unfilled cross-linked rubbers based on the concept of scission of polymer chains. The model is built up on the well-known Gent elastic potential complemented by a kinetic equation describing effects of polymer chain scission. The macroscopic parameters in the damage model are evaluated through the parameters for undamaged elastomer. Qualitative analysis of changing molecular parameters of rubbers under scission of polymer chains resulted in easy scaling modeling the dependences of these parameters on the damage factor. It makes possible to predict the rubber failure in molecular terms as mechanical de-vulcanization. The model was tested in tensile quasi-static experiments with both the monotonous loading and repeated loading-unloading.

The synthesis and characterization of polyamide-imides (PAI) derived from four different dianhydrides and three isomers of diaminobenzanilide are discussed with emphasis on the effect of combining an amide linkage in the diamine portion with other bridging groups in the dianhydride portion of the polymer backbone. It is noted that all of the amide-imide polymers exhibit high-glass transition temperatures, high thermooxidative stability, and a relatively good solvent resistance. These aromatic PAIs are characterized by high thermal stability due to chain stiffness, crystallinity, and intermolecular hydrogen bonding, and are considered to be good candidates as high-temperature films, coatings, and fibers for aerospace applications.

A nonlinear viscoelastic model based on the procedure of Findley et al., (1948) has been used to accurately represent the creep of several graphite/epoxy composites. Applying this approach to unidirectional 0, 90 and 10 deg off-axis tensile specimens, the viscoelastic response of a lamina can be characterized. The resulting lamina model has been useful for representing the behavior of a lamina in a numerical procedure to predict creep and delayed failures of general laminates. Also, independently, the Findley procedure has been used to characterize the nonlinear viscoelastic behavior of general laminates.

We present an experimental approach to discriminate hyper-elastic models describing the mechanical behavior of rubber-like materials. An evaluation of the displacement field obtained by digital image correlation allows us to evaluate the heterogeneous strain field observed during these tests. We focus on the particular case of hyper-elastic models to simulate the behavior of some rubber-like materials. Assuming incompressibility of the material, the hyper-elastic potential is determined from tension and compression tests. A biaxial loading condition is obtained in a multiaxial testing machine and model predictions are compared with experimental results.

An experimental program was conducted to study the thermochemical, flammability and toxicological characteristics of uncoated and coated polyisocyanurate foams. The coatings used were fluorinated copolymer and an intumescent material. Combustion and pyrolysis gases were analyzed by gas chromatography and mass spectrometry. The LD-50 and LD-100 tests were performed on Sprague-Dawley rats housed in an environmental chamber. The isocyanurate foam, fluorinated-copolymer-coated foam, and the intumescent-coated foam were found to have excellent flammability and insulation characteristics, although smoke development was substantial.

The thermochemical and flammability characteristics of laminating resins and composites currently in use and others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high-temperature laminating resins such as modified phenolics, polyimides and bismaleimides is compared with the performance of epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of the state-of-the-art epoxy resin and the advanced resin composites are detailed.

A study has been made of the origin of unexpected moisture effects on crack extension in fiberglass laminates. Water immersion has been found to greatly reduce the rate of crack growth under constant loading, while increasing the rate under cyclic loading, the latter effect being the expected one. Observations were made of the extension of the stable damage zone at the tip of precut notches in wet and dry environments. The damage zone size is postulated as a critical element in the relaxation of high stress concentrations in composites, such as those at notch or crack tips. Under constant load, moisture is shown to greatly expand the interply delamination region in the damage zone, thus reducing the local fiber stresses and increasing crack resistance. Under cyclic loading moisture has little effect on the delamination region, which is large even for dry environments, and the only effect is weakening of the material and acceleration of cracks. Severe hygrothermal conditions can so weaken the material that the crack resistance is reduced under constant loading as well.

Elongated metal or other conductive particles can be added to a polymer or other poor conductor to produce a composite of enhanced conductivity. Elongated particles are generally more effective than spherical or irregular particles but very slender particles can be dramatically more effective. For example, cylindrical copper particles with length/diameter (L/D) = 20, randomly dispersed in epoxy resin at a loading of 5 percent copper by volume yield a composite with a thermal conductivity about 1.5 times that of the base resin. However, the same volume of copper particles with L/D = 50 can increase the conductivity by a factor of 5 or more. This paper presents a new type of analysis for predicting the thermal conductivity of disperse composites from the properties of the component phases and elementary characterizations of particle shapes and orientation. This analysis successfully predicted the sensitivity to particle shape which was confirmed by experiments also reported in this paper. These results suggest that highly elongated particles may be used to achieve dramatic modifications of thermal conductivity and the analysis presented here may be a useful tool in the design or development of disperse composites of specific thermal conductivity. The analysis may also apply to other properties such as electrical conductivity or magnetic permeability.

Thermal conductivity measurements were made on polyethylene samples which had been crystallized at different temperatures in order to vary density and lamellar crystal thickness. Tests were also made on polyethylenes which were oriented by mechanical shearing and by crystallization in a temperature gradient. The thermal conductivity increased linearly by 50% as the density went from 0.96 to 0.99 gm/cc. By orientation the conductivity was increased ten fold in the direction of molecular orientation and decreased two fold in the perpendicular direction. For samples oriented by deformation at different temperatures, the conductivity apparently correlates with birefringence.

A theoretical analysis of the tensile stress-strain relation of elastomers at constant strain rate is presented which shows that the time and the stress effect are separable if the experimental time scale coincides with a segment of the relaxation modulus that can be described by a single power law. It is also shown that time-strain separability is valid if the strain function is linearly proportional to the Cauchy strain, and that when time-strain separability holds, two strain-dependent quantities can be obtained experimentally. In the case where time and strain effect are not separable, superposition can be achieved only by using temperature and strain-dependent shift factors.

Static stiffness, strength and ultimate strain after thermal cycling were investigated for graphite/Kevlar 49/epoxy and graphite/S-glass/epoxy angle-ply laminates. Tensile stress-strain curves to failure and uniaxial tensile properties were determined, and theoretical predictions of modulus, Poisson's ratio and ultimate strain, based on linear lamination theory, constituent ply properties and measured strength, were made. No significant influence on tensile stress properties due to stacking sequence variations was observed. In general, specimens containing two 0-degree Kevlar or S-glass plies were found to behave linearly to failure, while specimens containing 4 0-degree Kevlar or S-glass plies showed some nonlinear behavior.

Flow at the entrance of a tube or channel is of interest in many polymer processes. Except for mathematical treatments at high Reynolds numbers and in creeping Newtonian flow, one must turn to empirical correlating equations and qualitative observations. These are discussed in two parts, one on pressure drop and the other on flow patterns. The discussion of pressure drop is largely a review, dealing with inertial, viscous, and elastic contributions to the pressure drop in tapered and sharp-edged entrances; also presented are new data for a viscoelastic polymer solution in tapered cone entrances. In the section on flow patterns, stress birefringent data for a very elastic solution flowing into a channel entrance show an unusual effect: stress discontinuities, not unlike “shock waves,” upstream and downstream of the entrances. This is in contrast to Newtonian and less elastic materials in which the stress patterns change gradually between the developed flow region and the entrance region.

Samples of a filled elastomeric ablative material were stored at 45 C and 10 to the -6th torr for 7 months. Their tensile stress-relaxation modulus at constant strain was measured throughout the 7 months. Results of the testing are discussed primarily by comparisons of the data to atmospheric-pressure moduli (determined in this work for shorter periods of time) and with moduli predicted from short-time testing. Confirmation of the strengthening effects of vacuum on this composite was obtained. The use of time-temperature superposition techniques as an approximate accelerated testing procedure for this material under these conditions was also verified.

The study deals with the Payne effect (a substantial decrease in the storage modulus of a particle-reinforced elastomer with an increase in the amplitude of mechanical oscillations). The influence of temperature, concentration of filler and amplitude and frequency of strains is analyzed on the mechanical response of filled rubbery polymers. Constitutive equations are derived using the concept of two interpenetrating networks: one comprises semiflexible polymeric chains connected to temporary junctions, whereas the other is formed by aggregated filler clusters. Adjustable parameters are found by fitting experimental data for natural rubber, bromobutyl rubber and styrene-butadiene rubber reinforced by carbon black and polymeric particles. The critical concentration of particles is determined that characterizes transition from an ensemble of disjoint clusters to the network of filler. The volume fraction of filler corresponding to this transition is found to be close to theoretical predictions based on the percolation theory, as well as to experimental data for isolator-conductor transition.

The solubility parameters and molar volumes of substances can be used, in conjunction with suitable theory, to provide estimates of the thermodynamic properties of solutions; the solubility characteristics of polymer-solvent systems and the estimation of the equilibrium uptake of liquids by polymers are examples of the type of practical problems that are amenable to treatment. For low molecular weight liquids, the solubility parameter, δ, is conveniently calculated using the expression δ = (ΔEv/V)½, where ΔEv is the energy of vaporization at a given temperature and V is the corresponding molar volume which is calculated from the known values of molecular weight and density. For high molecular weight polymers, the volatility is much too low for ΔEv to be obtained directly and hence recourse must be made to indirect methods for estimating δ for these materials. One such widely used method is based on Small's additive group “molar-attraction constants” which when summed allow the estimation of δ from a knowledge of the structural formula of the material; however, the density must still be determined experimentally. The proposed method of estimating δ, also based on group additive constants is believed to be superior to Small's method for two reasons: (1) the contribution of a much larger number of functional groups have been evaluated, and (2) the method requires only a knowledge of the structural formula of the compound.

Four new fluoropolymers were pyrolyzed in a vacuum to study rates of volatilization and to identify decomposition products. The polymers thus studied were polyperfluoropropylene, polyperfluoroheptene, poly-4-chloroperfluoroheptadiene-1,6 and poly (1,2,2-triflluorovinyl phenyl ether). Polyperfluoropropylene yielded 100% monomer at temperatures of 300 to 400°C gave an activation energy of 56.6 Kcal/mole. Polyperfluoroheptenes of different molecular weights also yielded 100% monomer on heating. However, they had lower thermal stability than polyperfluoropropylene, but a higher activation energy and a higher pre-exponential factor. Poly-4-chloroperfluoroheptadiene volatilized at a rate of approximately 1% per minute at 380°C. There was very little monomer produced on thermal decomposition and an activation energy of 60 Kcal/mole was obtained from rates of volatilization at 362, 374, and 381°C. Poly (trifluorovinyl phenyl ether) showed a 25% carbonized residue at 500°C pyrolysis. The polymer decomposes into fragments containing very little monomer. Undesirable low molecular weight components in the polymer are still to be eliminated.

Results are presented of friction and thermal tests of molded polyimide and pyrrone polymers. The coefficient of sliding friction up to surface velocities of 2 m/sec (394 ft/min) and the coefficient of thermal expansion from 300 to 500 K (80 to 440 F) were measured. An apparatus was constructed to measure simultaneously the coefficient of sliding friction and the friction-generated temperature. Measurements were made at a nominal pressure-velocity product of 0. 25 MN/msec (7100 lb/in. **2xft/min) and at temperatures between 300 and 500 K (80 and 440 F). Despite the severe conditions, the polyimide and pyrrone performed well without obvious degradation.

It is pointed out that research efforts are at present being directed in two areas, one comprising experimental studies of this phenomenon in various glassy polymer systems and the other involving the development of a quantitative theory capable of satisfactorily predicting aging behavior for a variety of polymer materials under different conditions. Recent work in both these areas is surveyed. The basic principles of nonequilibrium behavior are outlined, with emphasis placed on changes in material properties with annealing below the glass transition temperature. Free volume theory and thermodynamic theory are discussed.

Addition polyirnide oligomers with nadimide end groups (I) have been synthesized from 4,4′-oxydiphthalic anhydride and 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride with several isomeric diamines and, nadic anhydride. The low molecular weight amic acid? and corresponding imides were isolated and characterized. Solubility and melt-flow properties of the imide prepolymers were studied to determine the applicability of the resins as adhesives and composite matrices. Thermomechanical transitions of the polymers were obtained by torsional braid analysis. Properties were compared with a similar addition polymer, P13N.

The cross-linked, ladderlike structure of cured pyrrones is not susceptible to forming at ordinary temperatures and pressures. At unusually high processing temperatures, of the order of 500°C, these intractable materials are observed to undergo transient flow sufficient to allow molding of the material. This observation, supported by analytical information, suggests that the flow occurs because of the breakage of covalent organic bonds and subsequent structural rearrangement of the cross-linked polymer network. This is in accord with a number of isolated reports of the pyrolytic behavior of several polymers.

This effort determined if enhancements to the properties of fully cured EPON 830-4,4′-Methylene Bis Cyclohexylamine epoxy resin systems (ERSs) could be induced by thermally curing them, while also simultaneously exposing them to economically generated magnetic fields (MFs). Stoichiometric mixes were cured for 5 hours at 121°C while being exposed to MFs between 0.1290 and 0.8810 Tesla. Exposed and control specimens were simultaneously cast from the same mix in each run. The resulting specimens were mechanically and thermally tested to find any property differences. This effort determined that under these conditions there were no modifications to the properties of MF exposed, fully thermally cured, ERSs relative to their controls.

Optimization of the deep-UV and electron-beam lithographic properties of a copolymer of trimethylsilylmethyl methacrylate (SI) and chloromethylstyrene (CMS), P(SI-CMS), within a weight average molecular weight range of 1.4 to 4.1 × 105 and 90 to 93 mole percent SI composition has been achieved. The solubility behavior of P(SI-CMS) resist was examined using the Hansen 3-dimensional solubility parameter model and dissolution rate measurements. Swelling of the resist has been minimized through the identification of a single component developer (2-propanol) and rinse (water) system. For the material containing 90 mole percent SI (14.9 weight percent Si) and M̄ω = 1.4 × 105, the sensitivity to 248 nm radiation is 65 mJ/cm2 and to electron-beam exposure is 3.4 μC/cm2 at 20 kV. This material Is applicable to bilevel lithographic processes, and the O2 reactive ion etching (RIE) rate is 16 times slower than standard hard-baked photoresist. Using a He/O2(60/40) RIE pattern transfer process, 0.4 μm line/space patterns have been resolved in a 1.3 μm bilayer structure for deep-UV exposures, and 0.25 μm imaging has been demonstrated in a 0.7 μm thick planarizing layer using electron beam irradiation. The loss in linewidth associated with the 0.25 μm process is ∼0.04 μm.

Materials and processing are described that provide 0.5 μm resolution with between 1 and 2 μm total depth of focus using a 436 nm stepper with 0.42 N.A., using the previously described PIE process (SPIE 631, 171 (1986)); 0.4 μm lines, spaces, and line/space gratings were reproduced. The chemistry is based on the photobleaching of anthracene derivatives in the presence of oxygen, followed by a deep-UV pattern transfer exposure under nitrogen. Although resolution and process control are quite good, the exposure time of 1.2 s is somewhat long due to the limited oxygen permeability of the chosen polymer; in addition the strong unbleachable absorbance of the deep-UV resist limits the usable thickness to ∼500 nm. Materials have been identified that promise to overcome both limitations, yielding thicknesses of 1 μm or more and exposure times less than 500 ms. Application to 365 and 248 nm imaging is also possible.

Ceramic reinforced polyethylene and polystyrene composites were prepared by melt mixing and hot molding techniques. Temperature stable low-loss Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-δ (CLNT) ceramic was used as the filler to improve the dielectric properties of the polymers. The relative permittivity and dielectric loss in the microwave frequency range were increased with increase in the ceramic loading. As the filler content increased from 0 to 0.50 volume fraction, the relative permittivity increased from 2.3 to 9 and dielectric loss tangent from 0.0006 to 0.005 for polyethylene-CLNT composite. In the case of polystyrene-CLNT composite, the relative permittivity and dielectric loss tangent increased from 2.1 to 10.5 and 0.0005 to 0.0032 respectively with increase in filler content from 0 to 0.50 volume fractions. The thermal stability of the relative permittivity of polymer ceramic composites was also investigated. The experimentally observed relative permittivity was compared with theoretical models. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers

This paper reports both experimental and numerical investigations on delamination mechanisms in [05, 905, 05] carbon fiber(CF)/poly(etheretherketone) (PEEK) laminate subjected to low-velocity impact. It was found that the CF/PEEK composite exhibits the same damage mechanisms as epoxy-based composites, but superior delamination resistance. For the crossply laminate, the impact delamination results from a Mode II interlaminar fracture process, and a close association exists between the interlaminar shear stress field and the delamination growth. The prediction of impact-induced delamination sizes is discussed.

The radiation-induced polymerization of n-tetradecafluoroheptene-1 was investigated at pressures of 8100, 11,900 and 17,100 atmospheres and temperatures between 90 and 267°C. The data are interpreted in terms of a free radical mechanism and the polymer has a low ceiling temperature. As temperature is increased, the depropagation step becomes important and reduces the rate of polymerization. Under some conditions transfer seems to be a significant part of the mechanism. Several radiation-induced polymerizations at high pressure were carried out with 1,1,2-trifluorovinylphenyl ether as well as one with 1,2,3,4,5-pentafluorophenyl 1,1,2-trifluorovinyl ether. The results suggest that transfer limits the molecular weight of the polymers.

The influence of fillers like clay, silica, and carbon black on the rheological properties of 1,2 polybutadiene has been studied using a capillary rheometer. Silica filled compound exhibited the highest viscosity and clay filled compound the lowest viscosity at all shear rates. The effect of filler loading and temperature on the Theological behavior has also been studied. Smooth extrudates were obtained in most of the cases and die swell was lower for silica and carbon black filled compounds than for clay filled compounds. Rheograms of different 1,2 polybutadiene systems have been found to merge into a master curve using modified viscosity and shear rate functions that contain melt flow index as a parameter.

This study investigates the curing kinetics, thermal properties and decomposition kinetics of cresol novolac epoxy (CNE) with two curing agents, 2-(6-oxido-6H dibenz(c,e)(1,2) oxaphosphorin-6-yl)-1,4-benzenediol (ODOPN), and phenol novolac (PN). In comparison with the conventional PN system, introducing ODOPN, a phosphorus-containing bulky pendant group, into CNE increases Tg by 33°C, char yield from 30% to 38%, and LOI from 22 to 31. The DSC curing study reveals that the Ea of the CNE/ODOPN epoxy can be obtained by Kissinger's method. The resulting Ea values indicate that the catalytic effect of EMI is insignificant on CNE/ODOPN but is marked on CNE/PN, whose Ea was reduced from 131.5 to 75.6 KJ/mole. This result may be caused by the fact that the symmetric diol attached to the 1 and 4 positions of the naphthalene ring in ODOPN sets up a steadily resonating structure and inhibits the catalytic action. Further investigating the conversion ratio with curing temperature yielded experimental data that agreed closely with Kaiser's model. The orders of the autocatalyzed reaction, m, and the crosslinking reaction, n, are close to 0.5 and 1.0, respectively, independently of the scan rate. Finally, the TGA decomposition study by Ozawa's method demonstrates that the mean Ea declines with the phosphorus content, because the easy decomposition of the phosphorus compound in the initiation stage facilitates the formation of an insulating layer. However, results in this study further reveal an increasing tendency for Ea with decomposition conversion for an ODOPN/PN mixture with the ODOPN content of over 50%, probably because of the retardation of gas diffusion by the insulating layer of phosphorus compound.

The NMR (nuclear magnetic resonance) and GPC (gel permeation chromatography) studies of the polymerization of maleic anhydride and 1,2-propylen glycol are reported. Assignment of individual groups was made and their concentration dependence on reaction time was established. The first step of the reaction is the formation of monoesters, which, immediately after the temperature increased, reacted to diesters. The reactivity ratio between the primary and the secondary hydroxyl group of 1,2-propylene glycol was 2.6:1. The concentration of water formed was followed as a function of reaction time by the Karl–Fischer method.

A differential scanning calorimetry study on a typical thermoplastic elastomer, syndiotactic 1,2-polybutadiene, crystallized from the melt is presented. Endotherms observed upon heating for samples isothermally crystallized from the melt exhibited a double melting profile. The peak temperature of the endotherm that appeared at a lower temperature (low endotherm) showed stronger dependence on the heating rate than that appearing at a higher temperature (high endotherm). The results of partial melting experiments demonstrated that the high endotherm is not affected at all by melting of only the crystals responsible for the low endotherm, indicating that the double melting behavior is due to the existence of two crystalline species with different stabilities. Structures and melting mechanisms of these two different crystalline species are discussed on the basis of the observed difference in superheating behaviors upon melting. The results on overall rate of isothermal crystallization are also presented.

1,2,2,-Trifluorovinyl phenyl ether and 2,3,4,5,6,-pentafluorophenyl 1,2,2-trifluorovinyl ethers have been prepared, and the nucleophilic reactions of the phenoxide and 2,3,4,5-pentafluorophenoxide salts with tetrafluoroethylene have been investigated. In general, it is some-what difficult to control the reaction so as to produce the desired olefinic monomer. Under truly anhydrous conditions and when other sources of active protons are avoided, the olefin is the chief product if excess tetrafluoroethylene is used. The monomer produced is very reactive with phenoxide ions, and the diphenoxyolefins are the chief secondary products. Both monomers failed to polymerize under normal, free radical conditions. With boron trifluoride an oily material was obtained from the trifluorovinyl phenyl ether. High pressure and gamma rays converted both monomers into polymers.

Vinyl polymers containing pendant acetal groups were synthesized using (2,2-dimethyl-l,3-dioxolan-4-yl)methyl acrylate (DMA) and (2,2-dimethyl-l,3-dioxo-lan-4-yl)methyl methacrylate (DMM), and were evaluated as negative electron beam (EB) resists. It was found that the EB sensitivity of polymers containing acetal groups in the side chain was higher than that of polymers containing acetal groups in the main chain. A high sensitivity of 3.6 × 10−8 C/cm2 was observed. Copolymers of DMA or DMM with styrene were also synthesized in order to improve the durability for dry etching process. It was found that the copolymers had an excellent dry etching durability and were adaptable to EB lithography.

1,3:2,4-Di 3,4-dimethylbenzylidene) sorbitol (DMDBS) is a known nucleator and clarifier for polypropylene (PP). It is also known that in the useful concentration range of roughly 0.2–2%, it forms nanofibrillar structures within the PP melt. The kinetics of the DMDBS solidification process within the PP melt and formation of the ensuing nanofibrillar structure are studied by in-situ small angle X-ray scattering (SAXS) analysis. The dynamic lag of the fibrillar structure formation kinetics and its temperature dependence indicate a nucleation and growth mechanism, controlled by the rate of nucleation. Examination of the polystyrene (PS)/DMDBS system indicate structure formation only in compounds containing 2.5% DMDBS, as evident in the rheological behavior. Light microscopy reveals that the fibrillar cross-section in this case is larger by an order-of-magnitude in comparison to the structure in PP. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers

This article deals with the characterization of high trans-1,4-poly(butadiene) (TPBD) prepared by means of an anionic polymerization using an initiator composed of alkyl aluminum, n-butyl lithium, and barium alkoxide. By controlling both initiator composition and polymerization temperature, a set of TPBD was prepared with well-known number of 1,4-trans units, molecular weight distribution, and average molecular weight. Analyses by differential scanning calorimetry and diffraction of wide-angle X-rays showed a direct relationship between the microstructure of the polymer and its thermal properties. By increasing the number of 1,4-trans units (70–90%), the crystallinity of the polymer was increased (10–30%); polymers with less than 65% of 1,4-trans units were amorphous, whereas TPBD with a number of 1,4-trans units greater than 80% were polymorphous and presented two endothermic transitions. Summing up, the results presented in this article indicate that cyclohexane solutions of alkyl aluminum, n-butyl lithium, and barium alkoxide allow produce polybutadienes with enough amount of 1,4-trans units to display a regular microstructure that makes them susceptible to experience-induced crystallization, likewise at a reaction rate similar to that observed for the commercial production of poly(butadiene) with n-butyl lithium. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers

The kinetics of non-catalyzed, acid catalyzed and alkyltin catalyzed polyesterification of adipic acid with 1, 3-butanediol as a model for polymeric ester synthesis was followed at 180°C and 215°C by monitoring of carboxyl, hydroxyl, and water content of the reaction system. The rate constants of the three processes were calculated using a simulation method. The process is kinetically controlled during the first 4–10 h (down to AV 20 mg KOH/g, conversion 95%) and then thermodynamically controlled by elimination of water from the system. Methyltin derivatives, especially trichloride, are more active catalysts but dibutyltin oxide can be used with good results. The model study suggests that addition of the catalyst at the beginning of the process and applying a vacuum (pressure 60 Torr) will reduce the reaction time in half, compared with adding catalyst at AV 20 mg KOH/g and using no vacuum.

A new bismaleimide monomer, 2-((4-maleimidophenoxy)methyl)-5-(4-maleimidophenyl)-1,3,4-oxadiazole (Mioxd), was designed and synthesized. The chemical structure of the monomer was confirmed by means of Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance (1H NMR) spectroscopy and elemental analysis, and its thermal properties were characterized using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Mioxd as a reactive modifier was blended with epoxy resin based on bisphenol A diglycidyl ether (DGEBA) in weight ratio of 5, 10, and 15%, using 4,4′-diaminodiphenyl sulfone (DDS) as hardener. The effect of Mioxd addition on the cure behavior and thermal properties of the blend resins was studied by DSC, TGA, and dynamic mechanical analysis (DMA). DSC investigations showed that the main exothermic peak temperature (Tp) of the blend systems did not obviously shift with increasing Mioxd content whereas a new shoulder appeared and gradually grew on the high temperature side of the exothermic peak. The results of DMA measurements exhibited the glassy storage modulus (G') and glass transition temperatures (Tg) increased as the Mioxd content was increased, the cured blends investigated were miscible and no phase separation occurred. Further, the thermal decomposition temperature first decreased and then increased, but the char yield at 600°C increased with an increase in Mioxd content. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers