Mechanisms and micromechanics of fatigue crack propagation in glassy thermoplastics

An iterative approach is used to estimate, from interference optics measurements, the variation of refractive index and, hence, extension ratio along the length of a craze at the tip of a fatigue crack. The finite element method is used to compute craze surface stress distributions which are found to be similar to those obtained for static loading. High extension ratios, in the range 6 to 8 for retarded fatigue crack growth in poly(vinylchloride), are attained in the craze fibrils at the crack tip before crack jump occurs. The craze thickens primarily by surface drawing during the early stages of its growth but in the later stages the fibril creep mechanism predominates. The critical fibril extension ratio is not reached in a single cycle, as in normal fatigue crack propagation, and crack jump does not occur until, typically, after several hundreds of cycles during which the fibrils accumulate considerable damage.Presented in part at the 7th Int. Conference Deformation, Yield and Fracture of Polymers, Cambridge, UK, 11–14 April 1988.     

Segmental orientation in entangled chains

Slip-link model of an entangled chain is used to calculate average orientation of chain segments. The results in the asymptotic regime of very long chains prove linear dependence of optical anisotropy on stress despite complex stress-strain relation. The linear stress-optical law is predicted both for a single chain and a model network subjected to uniaxial deformation. The calculated stress exhibits non-linearity in Mooney-Rivlin plot. Effects due to entanglements are proportional to assumed number of slip-links per chain.     

Chemical heterogeneity in emulsion copolymers of carboxylic monomers

Copolymer latices of butylacrylate (BA) with acrylic and methacrylic acid (AA and MAA) were prepared by batch type emulsion polymerization, and, for comparison, copolymers with identical monomer composition were prepared by batch type solution polymerization.The distribution of the carboxylic monomers in the latex particles and the serum was studied by density gradient and sedimentation experiments with the analytical ultracentrifuge. Dynamic mechanical measurements of films of these copolymers were used to determine the storage and loss moduli as a function of temperature. From these measurements the position and extension of the glass transition range on the temperature scale is obtained. For heterogeneous emulsion copolymers with two glass transition temperatures the distribution of the carboxylic monomer units in the different copolymer phases can be determined. Electron microscopy of ultra thin cross-sections of stained films gave further insight into the film morphology.The combination of the results obtained with the different methods gives rise to the following clues: In the BA/AA latices about 40% (by weight) of the total AA used in the recipe are found in the serum as a water soluble polymer, about 50% are found to increase the glass transition temperatureT _g of the bulk of the BA copolymer and, therefore, are thought to be incorporated into the interior of the latex particles, and the remaining 10% are, conclusively, located on the particle surface.In the BA/MAA latices no water soluble copolymer could be detected in the serum, about 90% of the MAA used is found in the bulk of the copolymer, and about 10% form a second hard phase on the surface of the latex particles.Dynamic mechanical measurements on the copolymer latex films show at least two phases with different glass transition temperatures: the bulk of the copolymer with a relatively low content of (M)AA units and a glass transition range at low temperatures, and a second (M)AA rich phase with a highT _g.The latter phase forms a honeycomb-like structure surrounding the packed latex particles. That results in a three-dimensional network of polymer with a highT _g extending throughout the latex film. In spite of the fact that this phase is built from a small fraction of the total copolymer only, it has a very pronounced influence on the performance behaviour of latex films.Dedicated to Professor Dr. R. Manecke on the occasion of his 70th birthday.     

Micromechanisms of failure in short-fiber-reinforced high-impact polystyrene under tensile loading

Injection-molded, short-glass-fiber-reinforced high-impact polystyrene was investigated under uniaxial tension with special attention to the effects of fiber and rubber concentration on fracture behavior. According to a fracture morphology study performed by polarized optical and scanning electron microscopy, crazes were consecutively initiated from rubber-styrene composite particles and from fiber ends. The rubber particles exhibited an intra-particle failure mode which resulted from the failure manner of the matrix becoming of a more brittle character with increasing fiber fraction. Fibers were surrounded by neigh boring growing crazes. Failure at the fiber-matrix interfaces proceeded with an increase in the number of crazes. With increasing concentration of the fibers, crazing at rubber particles appeared to be suppressed and crazing occurred more preferentially at the fiber ends, which accelerated a macroscopic fracture.Dedicated to Prof. H. H. Kausch on the occasion of his 60th birthday.     

Investigations of a series of nonionic surfactants of sugar-lipid hybrids by light scattering and electron microscopy

Sugar-lipid hybrids of the type C_nC_m were prepared by coupling an alkane chain (C_n) with a maltooligosaccharide (G_m) over an amide linkage. Coupling was performed with maltobionolactone (G₂) and n-alkylamine chains C_n withn=8,10,12,14,16, i.e. variation of the hydrophobic part of the molecule, and with hexadecylamine (C₁₆) and different maltooligosaccharides (G_m, m=2,3,4,6). The solution properties of the various products were studied by means of static and dynamic light scattering (LS) and by electron-microscopy (EM).The results may be summarized as follows: If the alkane chain is shorter thann=14, small spherical micelles with a radius of about 3 nm are observed. In time these micelles aggregate further to form increasingly larger spherical clusters which eventually precipitate. Long rod-like micelles form whenn 14. Contour length and chain stiffness were determined by applying theories of semiflexible chains. A qualitative confirmation of the light scattering results, i.e., micelle size and shape, was obtained from electron microscopy.     

Changes in electrokinetic properties of natural rubber latex after surface chemical modifications

High-ammonia latex concentrate prepared from doubly-concentrifuged fieldHevea latex was exhaustively dialyzed to remove any residual water-soluble non-rubber constituents. The specially purified latex was then treated with specific chemical reagents to modify the surface ionogenic groupings originally present on the latex particle surface. The electrophoretic mobility of the modified latexes was investigated as a function of pH. The change in electrokinetic properties of the surface-modified latex was explained in terms of chemical modification to the ionogenic groups of the adsorbed layer of proteins and long chain fatty acid soaps on the latex particle surface, the negative charges of which are primarily responsible for the colloidal stability of the latex. For comparison direct extraction of the long-chain fatty acid soaps from the specially purified latex by solvent was also carried out. Present results indicate that the number of carboxyl groups from the adsorbed long-chain fatty acid soaps plays a major role in the stabilization of the latex concentrate. In comparison the contribution of negative charges from the adsorbed proteins towards the stability of the latex is of less importance.     

Polypeptides mixed monolayers: collapse mechanism

The mechanism of the collapse process of monolayers of poly-L-alanine and of its mixtures with poly--methyl-L-glutamate was studied at the water/air interface at temperatures of 15°, 20°, 25°, and 30 °C.From measurements of the collapse surface pressure as a function of molar ratios and from the determination of the collapse kinetics, as well as from ellipsometrical measurements of the thickness of the film, the complete solubility of the components, even in the collapsed phase, was deduced.Furthermore, activation energies and values ofG*,H*, andS* in relationship to the kinetics of this process were deduced; it was shown that this process is constituted of a first phase of nucleation and of a second phase of growth both for the poly-L-alanine alone and for its mixtures with poly--methyl-L-glutamate.     

Structural changes in solvent-induced crystallization of quenched isotactic polypropylene

Solvent-induced crystallization of quenched isotactic polypropylene (iPP) films in dichloromethane, cyclohexane, carbon tetrachloride, and chloroform has been investigated.WAXD, density, and DSC measurements indicate that smectic iPP films undergo a complex rearrangement of the structure in these liquids, leading to a process of crystallization.Transport properties of the dried samples, after the solvent treatment, show that the first stage of crystallization involves, in addition to the smectic phase, a fraction of amorphous phase, while further crystallization regards only the smectic phase.The morphology of the crystallized samples has been investigated by transmission electron microscopy following permanganic etching. No change in the basic morphology is found, although local organization showing splaying and branching appears clearer in the solvent crystallized samples than in the starting smectic sample.     

Stability of modified surface CaCO3 in the non-polar medium

The adsorption isotherm of methacrylic acid (MAA) and polymethacrylic acid (PMAA) molecules on CaCO₃ were studied. The isotherm of (MAA) adsorption from cyclohexane was found formed from two steps, while that of (PMAA) from ethanol is formed from one step. The effects of surface modification of CaO₃ with (MAA) and (PMAA) in the sedimentation properties in a non-polar medium (cyclohexane) have been studied. It was found that the most stable suspension formed is concerned with monolayer surface coverage for the two adsorptives. Also, studies were made for the rheological properties of concentrated suspension of CaCO₃ modified with (MAA) and (PMAA) in a paraffin oil. The equilibrium flow curves of CaCO₃ modified with (PMAA) suspensions exhibit pseudoplastic characteristics, accompanied by some degree of complex thixotropy, while that modified with (MAA) exerts a thickening effect with rheopexy characteristics.     

Covalent immobilization of trypsin onto poly(2-hydroxyethyl methacrylate)/polystyrene composite microspheres by cyanogen bromide method and its enzymatic activity

Covalent immobilization of trypsin onto poly(2-hydroxyethyl methacrylate)/ polystyrene composite microspheres, produced by emulsifier-free seeded emulsion polymerization technique, was carried out using the cyanogen bromide method under various conditions. The highest enzymatic activities of the trypsin immobilized in this study against N--benzoyl-L-arginine ethyl ester and N--benzoyl-L-arginine-p-nitroanilide, as low-molecular substrates and casein as a high-molecular substrate, were high, as corresponding to 80%, 85% and 50% of those of free trypsin, respectively.Part C of the series Studies on Suspension and Emulsion.     

Influence of the exchangeable cations on stability and rheological properties of montmorillonite suspensions

The effects of NaCl and CaCl₂ on the colloid stability and rheological properties of Na- and Ca-montmorillonite dispersions were studied. The distribution of cations between the surface and the bulk phase was determined. For both of monocationic montmorillonite, the critical coagulation concentration were 250 mmol NaCl/dm³ and 2 mmol CaCl₂/dm³. The changes in the Bingham yield stresses of Na- and Ca-montmorillonite dispersions as functions of the NaCl and CaCl₂ concentration could be explained in terms of the surface excess amount and equilibrium concentration of the cations, the second electroviscous effect and the formation of a gel structure.     

Thermo-optical analysis as a complementary method in the study of phase transitions of thermotropic liquid crystalline polymer and its blends with polycarbonate

Differential scanning calorimetry (DSC) and thermo-optical analysis (TOA) were applied to study the phase transitions phenomena of thermotropic liquid crystalline polymer and its blends with polycarbonate. It was found that both methods are complementary. Glass transition temperatures of the blends of polycarbonate with liquid crystalline polymer were measured and discussed.     

Study of the thermodynamics of adsorption of hydrolyzed modified polyacrylnitrile

The thermodynamics of adsorption has been studied of hydrolyzed modified polyacrylnitrile (HMP) in water solutions with a concentration ranging from 0.25 g/l to 2.00 g/l on bleached sulphate and unbleached and bleached sulphite celluloses at temperatures of 0, 20, 40, and 60 C.It has been established that with the rise in temperature, the amount of adsorbed polymer —(HMP) decreases. The values of the enthalpy change are negative and show a linear decrease with the increase in the amount of adsorbed polymer. The adsorption equilibrium is defined by the logarithmic isotherm of Tjumkin, valid for uniform heterogeneous surfaces.With the increase in the amount of adsorbed HMP the values of the entropy change become negative and linearly decrease. A compensation effect has been noticed which results from the simultaneous action of the entropy and energy factors.The values of the change of the chemical potential for the three types of cellulose are negative and linearly decrease with the increase in the amount of adsorbed HMP and with the rise in temperature.     

Insoluble monolayers of irisresorcinol at the air/water interface

Monolayer properties of irisresorcinol [5-(cis-10-heptadecenyl) resorcinol] were measured at the air/water interface. TheA-T isobars of the monolayers at 10 and 15 mN/m gave two-dimensional thermal expansivities of 1.4 × 10^–4/K and 1.3 × 10^–4/K at a temperature span from 7–40 C, respectively. The- A isotherms of the material showed only a little dependence on temperature from 5–35 C and onpH except at highpH, where monolayers expanded by ionization of resorcinol headgroups. Some types of saccharose in the subphase exhibited a characteristic interaction with irisresorcinol in monolayers, and there is a possibility that this material will be used for molecular recognition of some saccharoses.     

Dielectric relaxation in polymeric solids Part 1. A new model for the interpretation of the shape of the dielectric relaxation function

A model is proposed which explains the shape of the dielectric relaxation function at the glass transition of polymers. The model is based on the idea that the molecular mobility at the glass transition is controlled by intra- and intermolecular interaction. In addition, a specific model for the local chain dynamics in amorphous polymer systems is used. According to the scaling hypothesis of molecular dynamics the model relates the high frequency dependence of the dielectric loss curve to the local chain dynamics and the low frequency dependence to the intermolecular correlation.     

Morphology and optical properties of liquid crystals embedded in polyester resin matrix

This paper reports on morphological, thermo-optical, and electro-optical results of UV-cured polyester resin film containing liquid-crystal nematic and cholesteric domains. Electro-optic measurements were performed in an applied d.c. electric field. The morphological structure of PDLC film is modified by the various methods of their preparation. Size-distribution curves drawn vs the duration of the initial cooling obtained for cholesteric liquid crystal domains are presented.     

Characteristic changes of pH during the alkalization of latex dispersions of the ethyl acrylate — methacrylic acid copolymers

The titration curves of latex dispersions of ethyl acrylate — methacrylic acid copolymers have a rather complex shape which indicates a strong dependence of the apparent dissociation constant of carboxylic groups on the degree of neutralization and copolymer composition. These dependences seem to be related to changes in the macroscopic structure (swelling and disintegration) of dispersion particles during alkalization.     

Polymethylmethacrylate and stearic acid compatibility in monolayers

Mixed monolayers of polymethylmethacrylate (PMMA) and stearic acid (SA) on substrates with different pH are examined at 25 °C.The spreading isotherms of the pure components and their mixtures in different molar ratios indicate a critical pH value of the support, above which the components are miscible.This limiting pH value, which is confirmed also by surface potential measurements, allows a sufficient ionization of the carboxilic acid.This study was supported by CNR and MPI.     

Compression studies on aqueous polystyrene latices

An apparatus, that allows simultaneous measurements to be made of excess osmotic pressure and optical diffraction of polymer colloid dispersions, has been constructed. Results are reported for monodisperse polystyrene latices at several salt concentrations. An interesting feature of the results is a clear indication of a co-existence region occurring with particles of 182 nm diameter in sodium chloride concentrations of 10^–4 mol dm^–3