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Notes: This investigation considers a hypothetical three-phase ordered composite to permit the design of a new material both stiffer and tougher than the matrix phase alone. The required elastic solution is greatly simplified and was based on a single layered inclusion in an otherwise infinite matrix under uniaxial tension. The solution presented is exact and generalized to accommodate any number of concentric layers of different thickness and composition.

Notes: Attempts to use low-cycle fatigue techniques derived from the work of Coffin and Manson to predict the fatigue performance of six diverse structural plastics are discussed. Through an analysis of dynamic property and thermal behavior studies of polymer samples in reversed-tension fatigue, an improved model for the polymer fatigue process has been proposed. Laboratory test data are presented illustrating the relationship between the various models.

Notes: It is postulated that property gradients exist at the interface forming an “interphase” between the insert and the matrix. Such gradients might be caused by partial solubility and diffusivity of the two phases comprising a composite. For simplicity, the “interphase” is replaced by a shell exhibiting averaged properties (Eshell = 1/2 Einsert + 1/2 Ematrix, etc.). An exact linear elastic solution was employed to evaluate stress fields throughout all regions. The possible effect of the “interphase” and its thickness on several physical properties of the composite are evaluated in terms of the particular stress fields.

Notes: An investigation of the dynamic mechanical properties of several molten polymers was performed using the Maxwell Orthogonal Rheometer. Relaxation spectra derived from experimental data for the terminal region of viscoelastic response indicate that as molecular weight distribution broadens, terminal relaxation phenomena associated with molecular disentanglement and translation extend over a corresponding wider frequency range. The same data indicate that a true maximum relaxation time beyond which no elastic response is observed exists for the materials studied. Moreover, the maximum relaxation time corresponds to the reciprocal of the frequency where the dynamic viscosity deviates from its zero-shear value. Thus an estimate of the time necessary for complete elastic recovery in polymer melts is readily obtained experimentally.

Notes: Tensile creep measurements were carried out on a commercial ABS polymer over a temperature range from 40 to 100°C at stress levels from 0.6 to 1.8 × 108 dynes/cm2. Experiments were conducted in a prototype of an apparatus designed to be compatible with digital acquisition systems. Analysis of the data indicated that application of the time-temperature super-position principle was of limited value due to the use of test temperatures near and below the effective glass transition temperature of the acrylonitrile-styrene component of the polymer. A strong stress dependence of the compliance was observed, even at relatively short times after loading. This was analyzed in terms of a model in which the height of the potential energy barrier to motion of the molecular flow unit is lowered by the application of stress. Analysis of the temperature dependence of the compliance at low stress levels indicated that the effective Tg of the acrylonitrile-styrene phase is about 85°C. The temperature dependence of the magnitude of the activation energy is considered as is the stress dependence of the glass transition temperature. Implications of short-time response in creep with regard to response under impact loading are pointed out. Practical application of results to the prediction of dimensional stability of molded parts is discussed as well as the limitations involved in extrapolation of experimental data to long times and high stress levels.

Notes: Fine structures of several plastic/rubber two -phase polymer systems were studied by means of direct observations of ultrathin sections under the electron microscope using osmium tetroxide staining and a hardening procedure developed recently by Kato. Samples used are several types of both ABS polymers and high -impact polystyrenes, and several PVC/rubber blends and the results were discussed in relation to their dynamic viscoelastic properties. It is suggested that these studies may fruitfully be extended to clarify the structure -to property relationships by use of this method.

Notes: The purpose of this paper is to describe a new deformation calorimeter, which is based on differential thermometry and uses a flowing gas stream as a heat transfer medium which allows it to operate under near-isothermal conditions. Also presented are some preliminary test measurements with a crosslinked polyurethane elastomer and crystalline polybutene-1.

Notes: Antiplasticizers are considered to be diluents which when added to polymers result in mechanical property behavior opposite to that of plasticization. The addition of antiplasticizers to certain polymers such as Bisphenol A polycarbonate, polysulfone, and polyvinyl chloride results in the elimination of the secondary loss transitions of these polymers. As a drop in modulus accompanies these transitions, their elimination results in higher tensile strength and tensile modulus. As secondary transitions are commonly associated with ductility and impact strength, their elimination also results in the observed embrittlement characteristics. The addition of anti-plasticizers to polymers also restricts the diffusion of penetrants resulting from the decrease of molecular flexibility in the polymer matrix.

Notes: A useful concept in polymer science is the degree of crystallinity - the fraction of the polymer that exists in a relatively ordered state. Methods of determination of the degree of crystallinity using density, infrared, thermal, N.M.R. and X-ray measurements are examined in light of modern notions of the structure of semi-crystalline polymers.

Notes: The changes occurring when polythene melts are subjected to shear, have been investigated using a rotating bob fitted into a ram extruder. In addition to chain scission, low density polythene exhibits reversible changes in mechanical and viscoelastic properties. The magnitude of the changes is controlled by total shear strain, and is related to molecular weight and long chain branching. The mechanism appears to be one of reversible disentanglement operating mainly on the large highly branched molecules. The work is relevant to various extrusion processes and to other long-branched polymers.

Notes: This investigation deals with the fatigue behavior of a group of thermoplastics fortified with discontinuous glass fibers dispersed by an injection molding process. The thermoplastics included nylon, polystyrene and polyethylene reinforced with short (1/8 in.) and long (1/2 in.) glass fibers.Several aspects of the fatigue behavior are included in the study. First, classical S-N curves were generated under fluctuating tension with R = 0.05 to show the loss of strength due to cyclic load application. Next, the extent of progressive fatigue damage was established by measuring the residual strength after cyclic loading. Finally, hypotheses pertaining to the fatigue mechanisms operative in all four materials were made based on microscopic examinations of sections removed from fatiguedamaged specimens.

Notes: Twelve polymers and copolymers reinforced with random short glass fibers are used for the study of the strength -composition relationship. Six of these reinforced systems are new and have not been reported elsewhere. The effect of fiber volume fraction on tensile and flexural strengths is related to the Kelly and Tyson equation. For each composition the strengthening factor, F, is calculated and discussed with respect to the structure of the polymer. One factor pertaining to the actual performance of fiber glass, fiber efficiency, K, has been extrapolated for the fiber glass used for this study. The effects of fibers on toughness and the Izod notched impact strength are discussed. It is the impact strength ratio and not the toughness which is used to describe the net result of reinforcement.The deviations between the wet and the dry strengths are used to illustrate the effect of the fiber -matrix interfacial bond. A new parameter, Δθ, is introduced to describe the effect of structure on the fiber -matrix interface. The effect of water at the fiber -matrix interface is further demonstrated through the determination of dielectric constant and dissipation factor of the composite before and after water immersion. The rule of mixtures was found to apply to dry electrical properties of composites.

Notes: The effects of shear stress on the crystallization kinetics and morphology of linear polyethylene and polybutene-1 were studied with the aid of a specially designed apparatus. With this equipment, it was possible to heat a thin polymer sample between glass slides to a melt temperature, quench the sample to a crystallization temperature, and then deform the sample in shear by applying a constant load to one of the glass slides. During the deformation, the crystallization process was observed and photographed under a polarizing microscope. Also, the displacement of the glass slide was simultaneously recorded which made possible a determination of the shear strain as a function of time.The results demonstrate that two phenomena may occur in the initially supercooled polymer samples in response to the applied shear stress. In one case, the sample deformed until it fractured, generally exhibiting no evidene of crystallization; in the other, the sample deformed until an inflection point was reached after which the sample became rigid. This latter phenomenon was attributed to crystallization.At low shear stresses, the inflection point was associated with the growth of spherulites which simply became large enough to bridge the glass slides and prevent further deformation of the sample. This generally occurred prior to the completion of the radial growth of the lamellae.At high shear stresses, however, no evidence of crystallization was seen in the microscope until the inflection point was reached. At this point, birefringence was observed in the sample. The resulting structure generally could not be resolved in the microscope, thereby indicating very profuse nucleation.The results obtained clearly demonstrate that the application of a sufficiently high shear stress to an initially supercooled melt has a substantial effect on the rates of crystallization of both polyethylene and polybutene-1. This was shown most dramatically at temperatures close to the melting point, e.g., both polyethylene at 130°C and polybutene-1 at 113°C, which require over 104 sec to crystallize under quiescent conditions, crystallized at approximately 0.05 seconds.The application of a shear stress to a polymer melt is envisaged as resulting in molecular orientation. In accord with the theories of Flory, and Krigbaum and Roe, the associated decrease in entropy of the melt may be considered to increase the supercooling. Under high stresses at which large increases in supercooling result, crystallization occurs more rapidy at the high temperatures and with polymers of lower molecular weight. At low shear stresses, the influence of temperature and molecular weight on the crystallization kinetics is essentially the same as that obseved under quiescent conditions.Observations through the microscope have shown that the application of a shear stress to a polymer melt leads to large increases in the number of crystalline structures formed and to the formation of oriented morphologies. This latter phenomenon arises due to nucleation lines formed by impurities and spherulites in the deforming melt. The impurities and spherulites apparently cause a disturbance which is thought to result in a local increase in stress of the melt and, hence, a local increase in supercooling. Lamellae then nucleate on these lines and grow out radially.

Notes: Detailed crazing behavior in several plastic/rubber twophase polymer systems was studied by means of direct observation of ultrathin sections under the electron microscope by employing osmium tetroxide staining and hardening procedure. Samples used are ABS polymer, high -impact polystyrene and several PVC/rubber blends. All of the systems investigated showed evidence of stress -crazing when under flexural stress. Relationships between the dispersed rubber particles and the crazing behaviors were studied, and the role of rubber particles in the toughening mechanism of plastics was discussed based on these observations.

Notes: The effects of temperature and penetrant activity on the sorption kinetics and equilibria of a series of alkanes in glassy, biaxially oriented polystyrene were studied. Normal isomers of pentane, hexane, and heptane cause crazing of polystyrene film samples at high penetrant activities (〉 0.85). Crazing kinetics are identical to the kinetics of Case II transport. Transport of these normal hydrocarbons in glassy polystyrene in the temperature range 25 to 50°C is markedly non-Fickian; limiting Case II transport is observed at activities in exces of 0.6. Sorption appears to be controlled by highly activated relaxation processes including primary bond breakage at these high penetrant activities. Fickian diffusion behavior is approached, however, as penetrant activity is reduced. Sorption of the branched isomers of these compounds does not result in polymer microfailure. The sorption kinetics of the branched isomers, although time dependent, appear to be controlled primarily by thermally activated diffusion rather than large scale polymer relaxations which control Case II transport.

Notes: Some of the thermodynamic and physical properties of crystals of linear polyethylene, formed from dilute solution are discussed. These properties include density, enthalpy of fusion, infrared absorption spectrum, selective oxidation and dynamic mechanical measurements. Despite the fact that electron microscopic examination reveals an apparent geometric regularity to these crystals, all these physical measurements yield a consistent interpretation in that they require about 15-20% of the chain units to be in a non-random conformation, and to form a disordered amorphous overlayer.Detailed studies of the experimentally observed relations between the crystallite thickness, crystallization temperature, and dissolution temperature (melting temperature in a dilute solution) are also presented. A thermodynamic analysis of the dissolution temperature-size relations, based on independently determined equilibrium solubility temperatures, indicates that the interfacial free-energy characteristic of the mature crystallites is significantly different from that involved in nucleation. The interfacial structures of the nucleus and the crystallites must, therefore, also be different. Size control by a nucleation process can be demonstrated from very general theoretical considerations. However, the detailed molecular structure characteristic of the nucleus cannot be specified solely from the fact that this process is size controlling.

Notes: Work at Stanford Research Institute on the deterioration of polymers is based on the assumption that aging in the light is the most serious problem and that it has at least three components that must be separated if we are to understand the overall process. We have started by measuring the production of free radicals on the polymer when pairs of t-butoxy radicals are generated from thermal decomposition of di-t-butylperoxy oxalate (DBPO) in bulk atactic polypropylene at temperatures approximating service conditions, 35-50°C. Our preliminary experiments have brought out experimental difficulties and have raised more theoretical questions than they have answered. Nevertheless, they show that the efficiency of production of polymer radicals is low and sensitive to the mobilities of the polymer chains. They also suggest that two kinetically different oxidation processes, with different dependencies on rates of initiation and with different susceptibilities to inhibitors, are proceeding simultaneously. The implications of these findings for results of some previous work and for design of improved accelerated tests is considered.

Notes: Starting with specific constitutive equations, methods of evaluating material properties from experimental data are outlined and then illustrated for some polymeric materials; these equations have been derived from thermodynamic principles, and are very similar to the Boltzmann superposition integral form of linear theory. The experimental basis for two equations under uniaxial loading and the influence of environmental factors on the properties are first examined. It is then shown that creep and recovery data can be conveiently used to evaluate properties in one equation, while two-step relaxation data serve the same purpose for the second equation. Methods of reducing data to accomplish this characterization and to determine the accuracy of the theory are illustrated using existing data on nitrocellulose film, fiber-reinforced phenolic resin, and polyisobutylene. Finally, a set of three-dimensional constitutive equations is proposed which is consistent with nonlinear behavior of some metals and plastics, and which enables all properties to be evaluated from uniaxial creep and recovery data.

Notes: Equations have been derived to convert Brabender flow curves to Instron flow curves for practical application purposes. The technique involved is simple and has been described and discussed in detail. Nine pairs of Brabender and Instron flow curves of three different high polymers, each at three operating temperatures, have been found to fit each other quite well. The converted Brabender flow curves overlap a part of the Instron curves and extend the shear range toward the Newtonian flow region. An important consequence of this work is that the Brabender Plastograph can now be regarded as a formal viscometer while still functioning as a miniature of the Banbury mixers used in industry. More work is being done to take advantage of this consequence.

Notes: Constant stress creep and recovery experiments were performed in the nonlinear range under combined tension and torsion on a tubular specimen of polycarbonate. Nonlinear viscoelasticity theory was employed to describe the test results. It was found that the first three orders of stress terms and a power function of time adequately described the experimental results. The modified superposition principle satisfactorily predicted the recovery following creep. Recovery was almost complete in several days following two hours of creep.

Notes: The physical optics of iridescent multilayered plastic films are analyzed theoretically relating the layer thickness, layer arrangement, and refractive index difference between layers to the reflection spectra for light at normal incidence. Very vivid iridescent and metallic-appearing films may be made by proper control of layer distribution.

Notes: Salts of polyacrylic acid can be fabricated in heated molds using mixed powders of polyacrylic acid and metal oxides. Because of the strong intermolecular forces in these polyelectrolyte salts, they have elastic moduli several times greater than the moduli of conventional plastics. They also have very low coefficients of expansion and high compression strengths. Composites containing metallic and inorganic fillers have also been made and their mechanical properties measured.

Notes: The dynamic thermal stability of rigid PVC resin compositions as determined from Brabender torque rheometer tests has a linear relationship of stability time and torque from which a practical measure of processability at a fixed torque can be derived. The stability time at 1500 m-g torque, t1500, has been used to characterize differences between PVC homopolymer and copolymer resins in tin, calcium-zinc, lead, and bariumcadmium stabilizer systems. In every case, the vinyl chloride-propylene copolymers are unique in giving substantial process-ability advantages.The logarithm of stability time at a fixed torque, t1500, is a linear function of intrinsic viscosity, [η], for PVC homopolymers, giving a single line function corresponding to the expression log t1500 = A + B [η]. The constants, A and B, vary with each of the four stabilizer systems, and are related to the effectiveness of the particular formulations used.The ratio of t1500 for copolymers to the basic t1500 value for PVC homopolymers at the same intrinsic viscosity (molecular weight) is a practical measure of relative processability, trel, which is characteristic of PVC resin types and independent of stabilizer systems.

Notes: Mercaptan and disulfide contents of modified cotton fabrics could be determined by application of Leach's polarographic method for wool, with minor modification.It was found that mercaptocellulose prepared by the reaction of tosyl cellulose and potassium thiolacetate followed by alkaline hydrolysis contained considerable amounts of disulfided in addition to mercaptain. Iodometric titration of mercaptocellulose gave a higher value of mercaptan than that obtained by the polarographic method. The mercaptan and disulfide contents and methylene blue uptake of the iodine-treated samples indicate that some of the mercaptan groups further undergo oxidation to acidic groups as a result of the iodine treatment.The spatial effect in the oxidation of mercapto groups in modified cotton is briefly discussed.

Notes: The catalysis of the reaction of n-butyl alcohol with isocyanates, using organometallic derivatives of lead, tin, and mercury, has been investigated. The rate of the reaction was measured by following the disappearance of the isocyanate absorption in the infrared. Phenyl, n-butyl, and cyclohexyl isocyanate were chosen to represent typical aromatic primary and secondary aliphatic isocyanates. Within the same series of catalysts, RnMOAc, the catalytic effect decreases in the order RHg 〉 R3Sn 〉 R3Pb; and in all cases R = aryl 〉 R = alkyl. The electronic effects of substituents on the aryl moiety are not pronounced. Changes in X of RnMX greatly affect the catalytic activity. The mechanism of organometallic catalysis of the alcohol-isocyanate reaction occurs via a template-type mechanism whereby the catalyst acts to complex both reactants in a catalyst phase allowing the reaction to occur with greater facility.

Notes: The polymerization of N-vinylcaprolactam in toluene, dioxane, chlorobenzene, dimethylformamide, and ethylene carbonate with various peroxides, perbenzoates and azobisisobutyronitrile as initiators at 60-80°C, was studied. Under these conditions azobisisobutyronitrile and tert-butyl perbenzoate have satisfactory activity as initiators. Under these conditions N-vinylcaprolactam polymerization in homogeneous solution is first order towards the monomer and 0.5 order towards the initiators.

Notes: A study has been made of the photolysis and photo-oxidation of phenoxy resin. Photolysis results in the evolution of hydrogen, methane, ethane, propene, propane, toluene, and the oxides of carbon. Also observed are increased yellowing, a rapid rise in gel content, and a decrease in intrinsic viscosity and elongation. Photo-oxidation causes similar changes, but produces oxidized chain fragments, more gel, and less yellowing as well as broad absorptions in the hydroxyl and carbonyl regions of the infrared spectrum. A free-radical mechanism is proposed in which both chain scission and crosslinking occur.

Notes: Glass transitions in certain polymer samples were detected as a step change in a DTA trace in the exothermic sense. This anomaly is explained as a manifestation of the volume relaxation shown to occur at the glass transition in internally strained samples.

Notes: It was found that an ion radical complex is formed by the reaction of carbon black with an alkali metal (Li, Na, K) in tetrahydrofuran. The graft copolymerization of styrene with carbon black was carried out using the ion radical complexes as initiator, and free polystyrene and carbon black-polystyrene graft copolymer were obtained. The identification of the graft copolymer with carbon black was carried out by fractionation and thermal degradation. The initiation activity of the alkali metals increased in the order Li 〈 Na 〈 K. The effect of the particle size of the carbon black on the graft copolymerization was studied.

Notes: From the viewpoint of continuum mechanics, and particularly the energy concept of fracture, adhesive and cohesive failures are similar. The essential difference involves the interpretation of the energy required to create new (adhesive or cohesive) surface area. A simple pressurized disk test is described for measuring the adhesive value for a bonded elastomer, and an application to a debonding problem in engineering design is given.

Notes: A study of the swelling of Acala 4-42 cotton in aqueous alkalis and acids has been carried out. The degree of swelling of the cotton in the reagents has been indicated by measurement of the variations in width of the cotton at its widest point. The nature of the swelling process whether interfibrillar or intrafibrillar has been deduced from microscopical and x-ray evidence. It has been shown that a similarity of shape of the swelling curves, i.e., an equal degree of swelling in the same or other reagents, does not imply the same mechanism of swelling. The results are more readily explained in terms of the crystalline-fibril theory than by the fringe-micellar theory, especially when high degrees of swelling have been achieved.

Notes: We have investigated the high temperature mechanical behavior of several unplasticized emulsion- and suspension-prepared whole polymers, and carried out molecular weight, molecular weight distribution, and branching characterization studies on these same materials. It is concluded that the easier workability of the emulsion product is probably due to the absence of a considerable amount of high molecular weight polymer in these as compared to suspension-prepared polymers of equal average molecular weight as reflected by intrinsic viscosity determinations of Fikentscher K values.

Notes: Capillary rheometer measurements show that stearic acid can be characterized as a normal lubricant. If the content of stearic acid is increased in rigid PVC formulations, the melt viscosity will decrease. This leads to a corresponding increase of shear rate and volumetric flow rate. The influence of calcium stearate is opposite to the normal characteristic of a lubricant. Increasing amounts of calcium stearate lead to an increased melt viscosity and a decreased shear rate and volumetric flow rate. In the extrusion of rigid PVC, the apparent “lubricating” effect of calcium stearate is probably due to the increased friction with resulting heat evolution and higher mass temperature, leading to a decreased viscosity of the plastic melt. This is in agreement with the results of the extrusion experiments. Both mass temperature and power consumption decrease when stearic acid is added and increase when calcium stearate is added to the formulation.

Notes: Studies on the peel behavior of pressure-sensitive tape comprising a polyester backing and polyacrylate adhesive have shown that, in peeling from a plane glass surface, three fundamentally different modes of peeling may be distinguished, depending upon the rate of pulling. At low rates, deformation by flow of the adhesive appears to determine the peel behavior and the peel force is strongly rate dependent. At high rates, little or no viscous deformation of the adhesive occurs and the peel force is independent of rate. At intermediate pulling rates, cyclical instability of made of failure involving alternate storage and dissipation of elastic energy in the backing, results in the phenomenon of “slip-stick” peeling, in which failure is jerky and regular. Results have been obtained which show how the pulling rates at which transitions from one mode of peel to another occur, and the peel force values for a given type of failure, depend upon such factors as molecular weight of adhesive, thickness of backing film, and angle of peeling.

Notes: The reactions of trans-2,5-dimethoxy-4′-aminostilbene with poly(maleic anhydride-co-methylvinyl ether) and trans-2,5-dimethoxy-4′-isocyanatostilbene with poly(oxy-1,4-phenyleneisopropylidene:1,4-phenyleneoxy-2-hydroxytrimethylene) yield polymeric systems which undergo rapid crosslinking upon short exposure to ultraviolet light. The extent of photocrosslinking as a function of exposure time was determined by the decrease of the trans-stilbene ultraviolet absorption at 350 nm.

Notes: Diethylaminoethyl (DEAE)-cotton has been reacted with epichlorohydrin (1,2-epoxy-3-chloropropane) neat, in alcoholic solvents, and in aprotic solvents at temperatures ranging from 25 to 95°C. Fabric properties and electron micrographs of fibers removed from these chemically treated DEAE cottons have been compared with those obtained when DEAE-cottons were treated under similar conditions with other halogenated 1,2-epoxypropanes, and with 1,2-epoxy-4,4,4-trichlorobutane. For comparative purposes, epichlorohydrin was reacted with an aminized cotton containing primary amine groups, with cotton containing quarternary ammonium groups, and with DEAE-cottons in which the tertiary amine groups had been quaternized. For reaction at 95°C with net epichlorohydrin, greatest increase in conditioned wrinkle recovery was observed with DEAE-cottons. Only with DEAE-cottons were the add-ons and recovery angles imparted by epichlorohydrin affected by the anion associated with the amine groups. None of the halogenated 1,2-epoxypropanes reacted with unmodified cotton in the absence of a basic catalyst. Those that reacted with unmodified cotton in the presence of an external base catalyst did not improve conditioned recovery angles. The mono-, di-, and trichloro-1,2-epoxypropanes all increased the conditioned and wet wrinkle recovery of DEAE-cotton when reacted neat at 95°C. The type of oxirane ring opening of epoxypropanes was shown to be influenced by the degree of chlorination of the carbon alpha to the ring. Both primary amine groups and quaternary amine groups catalyzed the epichlorohydrin-cellulose reaction. Dilution of epichlorohydrin with alcohols or decreasing reaction temperature lowered add-ons and improvements in wrinkle recovery properties. Use of aprotic solvents for the DEAE-cotton-epichlorohydrin reaction gave finished cotton fabrics having only high wet wrinkle recovery properties.

Notes: The reaction of hydrazine hydrate with manganic hydroxide and its application to the solution polymerization of methyl methacrylate has been studied. The kinetic evidence suggests that the hydrazine and the monomer are both adsorbed on the surface of the manganic hydroxide sol and that the decomposition of the hydrazine and the polymerization of the methyl methacrylate follow zero-order kinetics. The rate of polymerization increases slowly with increasing temperature, the activation energy for the polymerization being 4.9 ± 0.2 kcal/mole.

Notes: The properties of 4-methyl-pentene-1 polymer (TPX-RT-D30) were altered by blending petroleum jelly (P.J.) with the polymer. The polymer was blended with up to 40% by weight P. J. The plasticization of the polymer by the P. J. apparently allows high molecular weight fractions of the polymer to crystallize and influences the crystalline size and perfection. Tensile properties of the blends showed both a break and yield value in all ratios as compared to only a break value for the pure polymer. Breaking strength ranged from 4000 psi for the polymer to 1000 psi at 40% P. J. The samples had a “necking down” effect at 10% P. J. Modulus decreased from 1.8 × 104 (literature value 2.1 × 105) to 2.3 × 104 at 40% P. J. Brittle point values varied from above room temperature to 5°C at 40% P. J. The Vicat softening point ranged from 181°C for the polymer to 87°C at 40% P. J. Differential thermal analysis (Stone) showed a melting point depression from 235°C to 218°C at 40% P. J.

Notes: Curing reactions were investigated after the gel point, using infrared transmittance and reflection spectrophotometric techniques. In the system carboxyl-terminated polybutadiene (CTPB)/Epon X801 or Epotuf STF-6, catalyzed with Fe(III)-acetyl-acetonate (FeAA), at an equivalent ratio of carboxyl to epoxide groups, the final extent of reaction of COOH groups was found to be between 64% and 77% for eight CTPB samples. Increasing the ratio of epoxide to carboxyl groups (up to 1.6) resulted in an increase in the conversion, but the complete reaction of COOH groups could not be accomplished. The final extent of reaction also depends upon the functionality of the crosslinking agent. The lower the functionality of the epoxide, the higher the conversion of COOH groups. The use of chromium naphthenate as a catalyst for epoxide-COOH reactions gave higher conversions than FeAA. This result is related to side reactions catalyzed by the chromium naphthenate. The change in mechanical properties and the change in extent of reaction were followed simultaneously; it was found that no further development of mechanical properties occurred when the curing reaction between COOH and epoxide groups had ceased.

Notes: The thermal conductivity, specific heat, and dynamic mechanical behavior of an epoxide system have been investigated over a relatively wide temperature range. Effects of nonstoichiometric amine concentrations and postcure heat treatments were included in the study. The thermal conductivity behavior was found to be related to the extent of cure of the poxy system, but in general the results were typical of an amorphous polymer. Calorimetric determinations were used to study the curing reaction and the glasslike transition temperature for the various systems. Dynamic mechanical results were employed to delinearte the various internal relaxations of the cured materials and in some instances to permit correlation of relaxations with the thermal conductivity and the specific heat results. From comparison of present results to those of a previous paper, the activation energy for the relaxation process occurring near 270°K has been estimated to be 16 kcal/mole.

Notes: X-Ray diffractograms of cellophane showed a considerable variation in the intensity corresponding to the 101, 101, and 002 planes. Applications of generally accepted procedures for estimating crystalline content in cellulosic materials yields varying results for crystallimity in cellophane. It is concluded that such procedures are not applicable to cellophane used in this study.

Notes: Long-term weathering studies of the subject transparent thermoplastic polymer revealed that sheets extruded from pristine resine gradually became hazy. Electron microscopy of fracture surfaces showed that minute voids were created during outdoor exposure. By the application of the Mie light scattering theory, it was possible to calculate that the average void size was 4 × 103 Å and that the concentration of voids numbered about 106/mm3. Yet the total void volume of the poorest sample, which had a haze value of 26%, was less than 0.05%. The average void size decreased over a three-year period, but the concentration increased with exposure. A mechanism of void formation was formulated based on photo-induced moleculàr degradation. Chemical evidence suggests that molecular degradation occurs by complete unzippering of a molecule, resulting in the formation of carbon dioxide and 2,2,4-trimethylpentene-3-al. The aldehyde is believed to plasticize the polymer in the vicinity of a growing void and the carbon dioxide acts as a blowing agent, therby generating a void. Simultaneously, free radicals formed during molecular decomposition initiate further degradation of neighboring molecules. The propensity of this resin to haze can be effectively overcome by suitable cleanup and stabilization procedures.

Notes: Molecular weight distributions for polypropylene samples have been determined by a permeation fractionation method (GPC). Porous silica beads were used as a packing material for the columns. The set of columns allows a good separation of the polypropylene macromolecular chains in a range of molecular weights from 5000 to 1.5 × 106, and the thermal and mechanical stabilities of these beads are very good. The calibration has been carried out with fractions of polypropylene of narrow molecular weight distribution prepared by a large-scale column fractionation. The molecular weights M̄w and M̄n and the ratios M̄w/M̄n calculated from the GPC curves show, in general, good agreement with the ones calculated from the column fractionation curves. However, the M̄w/M̄n ratios are always highter in the case of GPC fractionation. This could be due to diffusion phenomena.

Notes: N-Substituted β-aminopropionhydrazides, RNHC2h4CONHNH2, were prepared by the Michael addition of primary amines to acrylic esters. The adducts were converted to the corresponding hydrazides. The aminohydrazides react readily with terminal epoxides at moderate temperatures yeilding B-stage resins of excellent storage stability. When powdered B-stage resins are sprayed on hot metal (150-230°C.), a smooth cross-linked coating is formed in less than 3 min. The coatings have unusually high elasticity, they pass the Olson button test. For best performance the amine used should have the primary amino group attached to either a primary carbon atom or directly to an aromatic nucleus. Aminohydrazides with the following R. Groups have been prepared: methyl, n-butyl, sec-butyl, tert-butyl, phenyl, cyclohexyl, benzyl, octyl, dodecyl, and octadecyl.

Notes: Continued shearing of molten long-chain branched acetal polymers raises their melt flow rates manyfold. The increase is not due to molecular degradation, as evidenced by constancy of inherent viscosity, and by the ability to reverse the increase by dissolving and reprecipitating the polymer. Shearing was found to have only a relatively small effect upon the melt viscosity but a very large effect upon the entrance correction for capillary flow. It is suggested that crystallization of branched polymers from solution creates an exceptionally strong entanglement network, and that the observed rheological changes reflect the disruption by shear of this network.

Notes: Based on a simple, general kinetic scheme for the inhibition reaction of a photopoly-merizing system, a solution is obtained for the differential equation which describes the oxygen concentration profile as a function of exposure time, light intensity, and absorption coefficient. The effect of the absorption coefficient on the oxygen concentration in a polymer slab is evaluated by numerical computation.

Notes: The influence of hydrogen bonding on the flow behavior of polymer melts at high shear rate has been investigated using a capillary extrusion rheometer. The systems studied were copolymers of ethylene and acrylic or methacrylic acid. Hydrogen bonding was found to substantially enhance both flow activation energy and viscosity level, as well as the degree of dependence of viscosity on rate of shear. It was also found that hydrogen bonding does not influence the critical shear stress for onset of “melt fracture.” The data support the view that hydrogen bonds act effectively as temporary (quasi-) crosslinks during the short time scales of deformation involved in flow at high shear rates.

Notes: Gamma radiation-induced graft polymerization to natural rubber in benzene solution (solution grafting), graft polymerization to natural rubber latex (Emulsion grafting), and emulsion polymerization of three vinyl monomers - styrene (St), methyl methacrylate (MMA) and acrylonitrile (AN), were carried out under air atmosphere to compare the radiation intensity exponent of each polymerization rate under air atmosphere with that under nitrogen atmosphere or under vacuum. The intensity exponents of the solution grafting both under air atmosphere and under exclusion of air were found to be numerals near one half. This indicates prevailing normal radical mechanism. However, the intensity exponents of the emulsion grafting under air atmosphere were found to be 0.94, 1.00, and 0.82 for St, MMA, and AN, respectively, and those of the emulsion polymerization under air atmosphere, 0.16 and 0.15 for St and MMA, respectively, although those of both emulsion grafting and emulsion polymerization under exclusion of air were found to be numerals near to one half except for that of emulsion polymerization of AN. For emulsion grafting, the initiating species is considered to be trunk polymer radical but the terminating species is assumed to be the radical(s) produced in the water phase in the presence of oxygen. For emulsion polymerization, both initiating and terminating species are assumed to be the radical(s) produced in the water phase in the presence of oxygen.

Notes: The oxidative susceptibility to different oxidizing agents such as dichromate-sulfuric acid, dichromate-oxalic acid and sodium hypochlorite in presence of leuco Cibanone Orange R of cellulose oxidized with sodium metaperiodate and its corresponding borohydride-reduced product was studied and compared with that of cellulose. From the changes in the chemical properties of the oxidixed products, an attempt was made to study the mechanism of oxidation of periodate oxycellulose and sodium borohydride-reduced periodate oxycellulose with the above mentioned oxidizing agents.

Notes: The extensive use of plastics for insulation and building materials has created interest in the possible toxicity of their combustion products. Three poly(vinyl chloride) homopolymers, a vinyl chloride-vinyl acetate copolymer, and formulations of two of the homopolymers and the copolymer have been examined to determine the composition and toxicity of their combustion products. Differential thermal analysis and thermal gravimetric analysis were used to study the breakdown process which occurred in several steps, the largest and first being the release of hydrogen chloride from the polymer at about 300°C. Approximately 50 products of combustion were then determined qualitatively by using either infrared spectroscopy or a combination of gas chromatography and mass spectroscopy. Quantitative analyses were carried out on 22 of the combustion products, and quantitative changes with varying air supply, temperature, and heating rate were determined. A comparison of the products of the polymers and their formulations is given.

Notes: Thermogravimetric and differential thermal analysis have been employed to study the effect on the thermal degradation pattern in static air of the molecular weight of poly(m-aminostyrene) homopolymers and copolymers with styrene. Related substituted styrene polymers and copolymers with styrene have also been studied in order to assess the effect of introduction of amino, substituted amino, and hydroxy groupings into a polystyrene main chain. The effect of these groupings on the thermal stability of the polymers as compared with polystyrene suggests that the inherent antioxidant characteristics of the subtituent grouping plays the major role in stabilization. A molecular weight effect has been shown to be operative for m-aminostyrene, p-N,N-dimethylaminostyrene, and m-hydroxystyrene polymers. This manifests itself in terms of different thermograms rather than by significantly influencing the procedural decomposition temperatures, although a trend is seen.

Notes: The rate of contraction of drawn nylon 66 in aqueous phenol was investigated, and a method is described for correlating this contraction with a series of elementary rate processes. The rate constants so obtained were analyzed by absolute rate theory, and the variations of ΔH† and ΔS† with phenol concentration gave evidence of the nature of the reaction steps.

Notes: The kinetic model for polycondensation reactions has been derived and techniques for validating the model have been described in Parts I and II of this work. This paper is concerned with using the results of Part I and II for the analysis and design of continuous polycondensation reactors.

Notes: A tensile testing device for measurements on polymer samples while immersed in a liquid is described. The temperature range is approximately -100 to +150°C. The sample older containing the immersion liquid is an all-glass container attached to a modified tensile testing device. The thermostatting and recording equipment is also described. Stress-strain curves obtained with monofilaments of regenerated cellulose immersed in n-pentane and liquid ammonia are shown. For filaments in n-pentane the variation of the modulus of elasticity with temperature down to -40°C is also reported as a further example of the applicability of the new device.

Notes: The effect of molecular weight on the changes in the surface layer of polystyrene films on near-ultraviolet irradiation has been studied in a nitrogen atmosphere at 25°C. Changes produced by irradiation were followed by determining the amount of solvent-insoluble portions, the molecular weight changes, and the intrinsic viscosity changes. Most crosslinking took place in the range of the transmissible depth of 2537 Å light. Low molecular weight samples formed a small amount of solvent-insoluble material. High molecular weight samples formed a large amount of solvent-insoluble material. In the range above a certain molecular weight, the amount of solvent-insoluble material approached an asymptotic value with increasing molecular weight, because of the limited penetration of 2537 Å light. Since most crosslinking took place in the range of the transmissible depth of 2537 Å light, the average number of crosslinks in the solvent-soluble portions was influenced by the amount of solvent-insoluble material. Low molecular weight samples produced many crosslinks. High molecular weight samples produced a few crosslinks. In the range above a certain molecular weight, the average number of crosslinks in the solvent soluble portions approached an asymptote with increasing molecular weight. Chain scission seems to have occurred in every sample.

Notes: Experimental data support the hypothesis that the surface layer of the asymmetric Loeb-Sourirajan type porous cellulose acetate membranes has a heterogeneous microporous structure. A general method is proposed for improving the performance of the above membranes in reverse osmosis, by which product rates are increased without decreasing solute separation. The method consists in pumping pure water past the back side of the membrane under just enough pressure for a sufficiently prolonged period of time; after such pretreatment, the membrane is used in the reverse osmosis experiments in the normal manner with the surface layer facing the feed solution. Back-pressure treatment at 400 psig for 85 hr on preshrunk and normally pressure-treated membranes increases the product rate by over 20% without decreasing solute separation in reverse osmosis experiments at 600 psig with the use of 0.5 wt-% NaCl-H2O feed solutions; with a different sequence of back-pressure treatment, similar results have been obtained in reverse osmosis experiments at 1500 psig also. The compaction effect of a normal membrane and that of a back pressure treated membrane are the same during continuous reverse osmosis operation under 600 psig; the effects of back-pressure treatment on a normal membrane and a compacted membrane are also the same. The pure water permeability data obtained in cyclic experiments show that the smaller pores on the surface layer are opened more than the bigger ones during the back side operation. The probable structural changes taking place in the film during back-pressure treatment are discussed.

Notes: The permeabilities of nitrogen, oxygen, and carbon dioxide through polyethylene-styrene graft copolymer films were measured by means of a gas permeability apparatus based on a modification of Barrer's high vacuum technique. Polyethylene-styrene grafts were prepared by mutual γ-ray irradiation of low-density polyethylene films in styrene-methanol solution. Densities and thicknesses of the graft copolymer films were determined. It was observed that the gas permeability constants decreased with increasing grafting to minimum values at 20-30% styrene grafting and increased again above 30% grafting. These results are explained in terms of a decrease in the free volume of the amorphous regions of the polyethylene by a “filling in” effect of the grafted polystyrene chains. Above 30% grafting, disruption of the crystallites may occur resulting in increased gas permeation. Activation energies for gas permeation through polyethylene-styrene graft copolymer films were calculated and found to decrease with increasing per cent styrene grafting. For nitrogen permeation, the activation energy decreased from 11.7 kcal/mole for unirradiated polyethylene to 9.5 kcal/mole for a 50.5% graft. Corresponding values for oxygen and carbon dioxide were 10.2-8.2 kcal/mole for a 48.7% graft and 8.4-6.5 kcal/mole for a 50.5% graft.

Notes: Chemical crosslinking of high-density polyethylene was studied. The amount of gel produced by a given peroxide concentration depends on the molecular weight of the polymer. More scission reactions, during the crosslinking process, occur in low-density than in high-density polyethylene crosslinked with Varox and Luperox 130 peroxides. The rheological behavior of partially crosslinked polyethylene is useful and convenient for quality control, for characterization, and for studies on the various mechanisms associated with the crosslinking process.

Notes: Present methods of correcting instrument spreading (resolution correction) in GPC are either too cumbersome to use or inaccurate when the correction is large. Two new methods which are both accurate and simple to use are presented in this work. The first method using the technique of Fourier analysis is more general and can be used to correct non-Gaussian instrument spreading. The second method using a fourth-degree polynomial requires a Gaussian instrument spreading function. The instrument spreading function may vary with respect to the elution volume in both methods.

Notes: Ruland's concept of an isotropic disorder function is applied to estimate the disorder parameter and the degree of crystallinity in a few cellulosic fibers: two cottons, native ramie, and a high-tenacity rayon. The results indicate an increase in disorder without any change in crystallinity on mercerization of native celluloses. On hydrolysis, with or without a pretreatment of mercerization, the samples exhibit a higher crystallinity, disorder remaining the same as for native celluloses. A ball-milled sample of “amorphous” cellulose is still found to be fairly crystalline with the lowest disorder. On being wetted in water and oven-dried, a distorted form of cellulose II with higher crystallinity and disorder was obtained. The polynosic fiber, Tufcel, has low values for the degree of crystallinity, disorder parameter, as well as crystallite dimension. A strong dependence of the degree of crystallinity on the crystallite size, particularly the lateral, is observed.

Notes: Low temperature gaseous plasmas of ammonia or nitrogen-hydrogen mixtures contain —NH2 groups, or precursors thereof, formed in the plasma, which experimental evidence strongly suggests, can add to various polymer surfaces. The plasmas were established in the 0.3-1.5 torr range by radiofrequency (13.56 MHz) electrodeless excitation at powers ranging from 50 to 500 W. Samples of polypropylene, poly(vinyl chloride), polytetrafluorethylene, polycarbonate, polyurethane, and poly(methl methacrylate) were investigated. All these polymers added amino groups to varying degrees of amino site densities depending on the choice of plasma parameters and the reactivity of the polymer itself. In every instance the polymer was rendered more wettable, although no quantitative wettability measurements were made. Following the plasma treatment, degrees of amino attachment to the polymer were followed radiometrically and reported in terms of “heparin thicknesses” resulting from ionic heparin —35S attachment to quaternary sites produced from the amino groups. Two implications of such a surface modification are to adhesion and blood compatible materials preparation.

Notes: The molecular orientation acquired during fiber formation of acrylic fibers by wetspinning has been studied. Orientation was detected by measurements of sonic modulus which were converted into an orientation factor. The orientation correlates very well with the ratio of take-up velocity to the freely extreuded velocity. Several mechanisms for the origin of spin orientation are discussed.

Notes: EPDM and SBR were masticated on an open mill. The temperature range of mastication for EPDM was 68-480°F. SBR was milled at 170-200°F. The gel-permeation chromatography analyses were made on the masticated samples. For EPDM at 68°F, molecular weight decreases and molecular weight distribution narrows with mastication time; the degradation process is nonrandom. At constant mastication time between 182 and 315°F, there is little change in molecular weight. Mastication for 18 min at 480°F broadens the molecular weight distribution; the degradation is random. For SBR at 170-200°F, molecular weight decreases and molecular weight distribution narrows with mastication time; the degradation process is also nonrandom. Nonrandom degradation for both EPDM and SBR results in a narrowing of the molecular weight distribution, without build-up of low molecular weight molecules, and without a shift in the peak molecular weight. This is contrary to nonrandom degradation of natural rubber where a shift in the peak molecular weight occurs with mastication time.

Notes: Investigation of the nucleating ability of selected nucleating agents in various commercial types of isolactic polypropylene revealed that the efficiency of individual additives is not equal for all types of polypropylene. As to the nucleation mechanism, it can be supposed that in most cases the added nucleating agents act mainly secondarily, activating the heterogeneities originally present in the polymer.

Notes: We consider two approaches to strain magnification in a composite material, point out that they apply to different situations, and caution against misapplication of the equations derived.

Notes: Latex dip adhesives for nylon and rayon tire cords are prepared by reacting resorcinol and formaldehyde in aqueous solution in the presence of a catalyst for a specified time and then adding a butadience-styrene-vinylpyridine latex. Ammonia improves the stability of the latex and increases the adhesion of rubber to cord. However, a white precipitate forms if ammonia is added before the resorcinol and formaldehyde have reacted sufficiently. This paper is study of the nature of this precipitate and the conditions for its formation. By measuring the heat of reaction of formaldehyde and ammonia and, subsequently, of mixtures of formaldehyde and resorcinol to which varying amounts of ammonia were added, information on the reaction mechanism has been obtained. Ammonia reacts rapidly with formaldehyde to form an unstable intermediate, presumably trimethylolamine, which then reacts further with resorcinol to form trisdihydroxybenzylamine. This compound is also very reactive and condenses withmore ammonia and formaldehyde to give a polymer of low solubility, the composition depending on the amounts of ammonia and formaldehyde available for reaction. Elemental analyses support this concept. Primary and secondary amines react in a maner similar to ammonia.

Notes: Untreated and fire-retardant-treated white α-cellulose samples were isothermally pyrolyzed in a fluidized bath in a nitrogen environment at 298-360°C. Results were reported in terms of volatilization (based on weight loss-time measurements) and the degradation products (based on gas chromatographic-mass spectrometric analysis). The findings products (based on gas chromatographic-mass spectrometric analysis). The findings on untreated cellulose indicate that: (1) pyrolysis occurs in three distinct phases in the temperature range 276-360°C; (2) there is a single activation energy of 42 kcal/mole over this temperature range; (3) the initial rapid weight loss is not due to the desoprtion of water, but primarily to decomposition of the cellulose; molecules: (4) there is little difference in either the quality or relative quantity of the volatiles generated during the three different phases of pyrolysis. The findings on treated cellulose show that the fire retardant, KHCO3, does not markedly change the types of degradation products having molecular weights below about 110, althought it does change their relative concentrations. Furthermore, the rate of product generation and the quantity of residual char are increased.

Notes: Epoxy-Versamid specimens were loaded in tension, compression, and flexure at different strain rates and temperatures to determine mode of failure, yield stress and strain, and tangent and relaxation moduli. Stress-strain curves were used to define brittle, ductile, ductile-rubbery, and rubbery modes of behavior which prevailed in different temperature-strain rate regions. The time-temperature superposition principle was applied to yield stress, initial tangent moduli, and relaxation moduli data for all three types of loading.The transition regions, tangent and relaxation moduli, and shift factors were the same in tension, compression, and flexure. Thus the most convenient mode of loading can be used to determine the general time-temperature dependence. The ratio of compressive-to-tensile yield stress was almost constant over the entire ductile region. Flexural yielding data were used to predict yield stress in tension and compression, and stress relaxation master curves were shown to be related to elastic modulus vs. strain rate curves. The yielding phenomenon was interpreted using Eyring's theory of non-Newtonian viscoplastic flow. The apparent activation energy and activation volume were larger for tension than compression. A theory is offered to explain why yielding can occur in a cross-linked system.

Notes: The development of new and more sensitive techniques in thermal analyses aids in a more complete understanding of the contributions of individual components in urethane elastomers regarding their mechanical and thermodynamic behavior. The behavior of various segments of the elastomers reported in this work illustrates a clearer interpretation of reasons for changes in mechanical behavior caused by changes in heat capacity, volume and tensile properties; the gross changes previously reported for polyurethane properties as a function of temperature are also confirmed with a more exact definition of their origin.The sub-ambient temperature behavior and response of physical measurements near the melting point of the backbone polyol are largely a function of the so-called “soft block.” The soft block does not contribute to the mechanical properties above the melting point of the polyol unless some urethane segments from the diisocyanate and extender are structured into the soft block, that is, excess diisocyanate and extender are added to build in the “hard” block. The extender and isocyanate influence for both low and high temperature properties is observed by the lack of molecular fit imparted to the backbone polyol as well as some crystallinity in the polymer hard block. The usual Tg transition reported in urethane elastomers corresponds to a first-order transition in the polyester or polyether backbone.

Notes: The effects of a number of sulfur compounds on the melt stability of polypropylene milled at 165°C have been studied. Dilaurylthiodipropionate (DLTP), Mercaptobenzimidazole (MBI), and Mercaptobenzthiazole (MBT) are all antioxidiants in a polymer lightly stabilized with a phenolic antioxidant although the last two are initially pro-oxidants. 2,2′-Dibenzoylaminodiphenyldisulfide (22BDD) is a pro-oxidant under the Conditions studied.In the absence of a phenolic antioxidant the effectiveness of DLTP is reduced in the early stages of oxidation, with increasing concentration although its over all antioxidant activity increases. The results are consistent with the view that both radical and non-radical processes occur concomitantly.

Notes: The preparation of the acetaldehyde polymers (PACH) having a poly(vinyl alcohol)-type structure and the thermal degradation of PACH have been reported previously. This paper will describe detailed aspects of several reactions of PACH. Copolymerization of PACH with toluene diisocyanate (TDI) was performed both thermally and catalytically. When piperidine was used as catalyst, the rate of reaction between PACH and TDI was found to depend on the concentration of both the active hydrogen of PACH and the isocynante group TDI. Acid and alkali treatment of PACH were carried out. On treatment with sulfuric acid, white polymers with good spinnability were obtained. The copolymerization of acetaldehyde with n-butylaldehyde were performed in the presence of sodium amalgam as catalyst. The reaction products were colorless, viscous liquids and assumed from the infrared and NMR spectra, elemental analyses, molecular weight and solubility tests to be aldol condensation-type copolymers.

Notes: A novel technique for the control of continuous synthesis of addition polymers with precisely controlled average molecular weight and minimum polydispersity has been developed. A control system adjusts the concentration of chain-transfer agent in the reactor feed to compensate for all other upsets, in the reactor inputs: initiator and monomer concentrations, temperature and feed rate. The technique has been evaluated quantitatively on a digital computer using a kinetic model of homogeneous, free-radical solution polymerization. In computational tests, the modeled control system generally held the instantaneous number-average chain length within 1%, and quickly returned it to the desired value in response to a wide variety of upsets. By generalizing the Schulz distributions to include termination by disproportionation, combination and chain-transfer, it is shown that changes in the molecular-weight distribution resulting from the action of the control system are minor.

Notes: A new-method of interpreting GPC chromatograms which accounts for skewing and symmetrical axial dispersion has been developed. General relationships for a symmetrical axial dispersion correction and for a skewing correction are derived.The method has been verified experimentally for unimodal chromatograms and linear calibration curves over a wide range of GPC operating conditions, polymer molecular weights and polydispersities. Measurements of h and skewing factors were obtained by a once-through technique. The need for performing reverse flow experiments has been eliminated. Artificial oscillations in the corrected chromatogram due to step size (Method of Pierce-Armonas), and to number of terms in a polynomial expansion (Method of Tung and Method of Smith) are eliminated.The method has yet to be evaluated for nonlinear calibration curves and multi-modal distributions. However, suggestions for its application in these circumstances are presented.

Notes: Difluorocarbene (difluoromethylene, :CF2) generated by the pyrolysis of sodium chlorodifluoroacetate has been shown to irreversibly modify the surfaces of polymers and fibers. The critical surface tension values of several polymers are shown to decrease with increasing exposure to difluorocarbene vapors and ultimately approach the critical surface tension values of partially fluorinated polyethylenes. The rate-controlling step appears to be the diffusion of difluorocarbene from the precursor to the polymer substrate. The nature of the interaction between difluorocarbene and the polymer surface is unknown; however, the absence of infrared bands due to C—F bonds in attenuated total reflection measurements tends to establish the mono-molecular-like character of the modified surface.

Notes: Study was made concerning both the rate of crosslinking and the structure of crosslinks of terpolymers that have dicyclopentadiene, 1, 4-hexadiene, methylene norbornene, and ethylidene norbornene for termonomers so as to look into the role of termonomers during crosslinking of ethylene propylene terpolymers. In the study, activation energy and frequency factor, both apparent were determined by the rate constant of crosslinking and differences in crosslinks were analyzed following both chemical and physical methods. Infrared analysis into the volume of consumption of double bond was adopted to examine the manner of crosslinking. In respect to the magnitude of the rate constant, ethylidene norbornene came in first being followed by 1,4-hexadiene, methylene norbornene, and dicyclopentadiene. The structure of termoners affected the apparent activation energy and the apparent frequency factor was subject to the influences of said structure and others including the variation in the degree of unsaturation. During the early stage of crosslinking, the formation of the crosslink of polysulfide-type was paramount to all others and the speed of conversion therefrom either to disulfide-type or to monosulfide varied with the kind of terpolymers and was in proportion to the rate constant of crosslinking.

Notes: The effects of crystalline modification of cellulose and of water on the ESR spectra generated by the trapped free radicals in gamma-irradiated celluloses were investigated for cotton cellulose I, II, III, and IV, partially decrystallized cotton cellulose, ballmilled cotton cellulose, hydrocelluloses of cellulose III and IV, and ramie. On irradiation of the celluloses, free radicals were formed on the cellulose molecule, probably following dehydrogenation or chain cleavage. The free radicals located within the less ordered or amorphous regions of the cellulose reacted readily with water and were terminated. The radicals located within the more ordered regions of the celluloses could be made accessible to reaction with water by the interaction of the celluloses with solvents which caused dimensional changes in the cellulosic structure. In the highly ordered regions of the celluloses, even after long periods of time in solvents which caused large dimensional changes in the cellulosic structure, the trapped free radicals were not terminated by reaction with solvent or water. The ESR spectra of the irradiated, dried celluloses were determined at -160°C, the single-line spectra recorded had line widths of about 18-24 gauss. On the absorption of water by the irradiated celluloses, the ESR spectra changed and were dependent on the crystalline structure of the irradiated celluloses. The effects of different arrangements of the irradiated celluloses, as shown by their trapped radical spectra, particularly after interaction with water, were discussed.

Notes: Carbethoxycarbene, carbethoxynitrene, and nitrene generated respectively by the pyrolysis of ethyl diazoacetate, ethyl azidoformate, chloramine and sodium hydroxyl amine-o-sulfonate are shown to irreversibly modify the surface of polyethylene as shown by wettability measurements. The nature of the modification is not fully understood; however, insertion of the carbene or nitrene into a carbon-hydrogen bond appears likely. The modified surfaces thus formed are shown to undergo several classical organic reactions as again determined by wettability measurements.

Notes: Vinyl esters of some undecylenic acid derivatives and acrylates and methacrylates of undecyl and undecylenyl alcohols, which may be considered as derivaties of castor oil, have been polymerized and copolymerized with vinyl chloride to provide a variety of new polymers. The acrylate and the methacrylate of undecylenyl alcohol have been epoxidized to yield two new polymerizable monomers of potential usefulness as crosslinking agents in finished copolymers.

Notes: The effect of the extent of degradation of poly(m-aminostyrene) on the quantity and composition of the residue and the effect of pyrolysis temperature on the fraction volatile at pyrolysis temperature are discussed. The behavior of poly(m-aminostyrene) is compared to that of polystyrene; a significant difference has been found for the behavior of the residue from poly(m-aminostyrene), which is ascribed to a crosslinking reaction involving the amino substituent. Mechanisms to acount for the observed products of degradation have been suggested and are discussed. Relative thermal stability studies have also been made and compared with results from polystyrene.

Notes: Studies were carried out on decomposition of hydrogen peroxide by ferrous and ferric ions adsorbed on cellulosic materials (SP, SCP), scission of the cellulose chain and formation of grafts by graft copolymerization. As a result, it was found that the activity of ferrous ion is always higher than that of ferric ion, but there exists a common relation between the amount of decomposition of hydrogen peroxide and the number of grafts for all cellulose samples and kinds of metallic ions, and it was inferred that essentially, copolymerization takes place by the same mechanism irrespective of the kind of metallic ions. Consequently, it can be considered that the difference in degree of activity between ferrous ion and ferric ion is due to the difference in the decomposition mechanism of hydrogen peroxide by these metallic ions and it is assumed that the high activity of ferrous ion in graft copolymerization is due to the high hydrogen peroxide decomposition effect.

Notes: The method of stress relaxation has been used to study stress decay behavior in the system of polyethylene - benzene series hydrocarbons. The behavior of stress decay in polyethylene under benzene series hydrocarbons was observed and the respective activity forward stress decay of benzene series hydrocarbons was obtained.

Notes: An addition reaction of maleic anhydride with polypropylene takes place in the presence of radical reagents or sunlight. The initial rate of the reaction was proportional to the concentration of polypropylene and maleic anhydride, and one-half power of the concentration of the radical reagents. The increase in the temperature from 80 to 120°C increased the rate of the reaction and di-cumyl peroxide was effective as a radical reagent for this reaction.Ionic crosslinked rubber-like polymers were obtained from the reaction of maleic polypropylene with some alkali metal compounds. They showed the characteristic absorption band due to —COO⊖ in their infrared spectra.

Notes: The stress cracking of polyamides (nylons) by a number of metal salts, in aqueous and nonaqueous solutions, has been investigated. Many metal halides and halide-like salts were found to be active stress-cracking agents, while metal acetates and sulfates were inactive. Zinc chloride was found to be most active, and its activity was compared with other metal halides. Using a recording tensometer, time to crack initiation, time to crack-through and time to rupture were determined. These parameters were found to be dependent on temperature, moisture content of the nylon, concentration of the cracking agent and level of stress. High values of all these factors favored rapid cracking. Cracking parameters were shown to be mainly independent of the surface geometry of the nylon and the hydrogen ion concentration of the cracking agent. Metal halides did not appear to cause any chain scission in the nylon and stress cracking was not due to hydrolysis or metal-ion catalysed hydrolysis.

Notes: The iron chloride-catalyzed radical chain addition of carbon tetrachloride to 1,4-polybutadiene has been studied. Transparent film forming nonflammable polymers are obtained which contain 50-55% chlorine. Cyclization appears to accompany the addition of carbon tetrachloride as an integral part of the radical reaction.

Notes: An effective copper surface treatment for adhesive bonding of copper foil and diallylphthalate resin was investigated.It involves dipping the copper foil in the potassium dichromate-sulfuric acid solution (K2Cr2O7:76 g/l, H2SO4:0.67 N) at 60°C for 5 min. The dichromate treated copper foil and glass based prepregs of diallylphthalate resin were laminated under the pressure of 38 kg/cm2 for 30 min at 145°C.Interface characteristics of the dichromate treated copper foil and diallylphthalate resin were examined.It was found that chromium is formed on the surfaces of the treated copper foil, and allyl groups in diallylphthalate molecule are oriented to the atoms, that is, the adhesive bonding is performed by the chemical affinity of chromium and allyl groups.The allyl group has a delocalized π-electron system, and that its bonding to a transition metal as chromium is appropriate and justifiable by quantum chemical considerations.

Notes: A method for measuring the surface energy of solids and for resolving the surface energy into contributions from dispersion and dipole-hydrogen bonding forces has been developed. It is based on the measurement of contact angles with water and methylene iodide. Good agreement has been obtained with the more laborious γc method. Evidence for a finite value of liquid-solid interfacial tension at zero contact angle is presented. The method is especially applicable to the surface characterization of polymers.

Notes: Mechanical and solution properties, melting transitions, torsional stiffness temperatures, Tf, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of Tf for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.