Mechanical and morphological investigations of UHMWPE/Fe composites

Ultra-high molecular weight polyethylene/iron composites were investigated. The specimens were obtained by pressing in a steel die and sintering at different temperatures. By means of porosimetry, microscopy, microhardness, density, and partial volumes of the components it is shown that there are no microcavities. The microhardness does not depend upon the weight % content of the metal in the composites. It also neither depends on the pressure nor the temperature of sintering. For low metal content within the composites, microhardness Mayer equations are linear. For high metal content the dependence is nonlinear. With the increasing of the iron content tensile strength weakly decreases. However, plane-strain compression, dimension steadiness, Vicat softening temperature, and tribometric characteristics of the composites are improved. It is shown that the polymer is a well-dispersive medium. The particles of the components have a good mechanical compatibility. The polymer wets the surface of the iron; this is probably connected with the surface oxidation of the metal particles.     

The spinnability of viscoelastic solutions of tetradecyl- and hexadecyl-trimethylammonium salicylates

The spinnability was measured for aqueous viscoelastic solutions of tetradecyl- and hexadecyltrimethylammonium salicylates (C₁₄TASal, C₁₆TASal) in the absence and presence of sodium salicylate (NaSal) and sodium bromide (NaBr). The spinnability is classified into two types, D and C. While the intrinsic drawing length in type D is proportional to the drawing velocity, the drawing intrinsic length in type C decreases with the drawing velocity or is independent of it. The spinnability changes from type D to C, as the drawing velocity and the surfactant concentration increase, and the temperature lowers. The effect of salt is different between NaSal and NaBr. It can be assumed that a pseudo-network structure composed of rod-like micelles is formed in viscoelastic and spinnable surfactant solutions. Then, the spinnability depends on the balance between the elasticity and the viscosity in which the structure results.     

Effect of plasticizer concentration on the hysteresis,tear strength and stress-relaxation characteristics of black-loaded rubber vulcanizate

The effect of plasticizer concentration on the stress softening, tear strength and stress relaxation of black loaded bromobutyl rubber vulcanizate has been investigated. The stress softening in the rubber vulcanizate, an energy dissipative process at higher strain, may be explained primarily by changes that take place in the rubber phase of the filled vulcanizate. Increased plasticizer concentration leads to decrease in the equilibrium hysteresis. A quantitative relationship between energy density and hysteresis has been derived, which is applicable at and below the elongation at break. Increase in plasticizer concentration results in decrease in the effective diameter of the tip of the tear, which in turn decreases the tear strength. Rate of relaxation decreases with increase in the plasticizer concentration in the carbon-black-filled vulcanizate.     

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.     

Preparation of muscovite with ultrahigh specific surface area by chemical cleavage

The specific surface area of a muscovite sample increases drastically after exposure to a LiNO₃ solution, e.g., from 3.4 m²/g, corresponding to platelets of ca. 200 silicate layers, to 295 m²/g (platelets of ca. 2–3 silicate layers) after treatment at 180°C under atmospheric pressure for 46 h. The efficiency of the cleavage process decreases with decreasing temperature (down to 50°C). The LiNO₃/H₂O weight ratio is also very important: at 130°C and a reaction time of 46 h, for instance, a value in the range of 1.7–1.8 leads to the highest specific surfaces. The cleaved products have the form of strong papers that disperse readily in water. During the cleaving procedure, not only the particle thickness, but also the diameter decreases. There is no evidence of damage or partial dissolution of the silicate structure after cleavage, by IR spectroscopy and yield. The use of LiCl also leads to an increase in specific surface area, but the effect is weaker than in the case of LiNO₃. Treatment with some other alkaline and alkaline earth nitrates and chlorides did not increase the specific surface area of muscovite significantly.     

A study of the ageing of the gel structure in a nonionic O/W cream by X-ray diffraction,differential scanning calorimetry and spin-lattice relaxation measurements

The time dependent changes of the lamellar gel structure in a nonionic O/W cream were studied. It appeared that the changes were connected with alterations in the hydrophilic layers of this lamellar gel structure. The structure of the hydrocarbon layers did not change. The alterations were induced by an increasing hydration of the surfactant molecules on cooling from the preparation temperature to room temperature. Ageing of the cream involves a decrease of the thickness of the hydrophilic layers and a change of the distribution of the surfactant molecules, resulting in, among other things, a decrease of the release rate of a hydrophilic drug. Ageing of the cream can be prevented by using the appropriate amount of starting materials or by the use of polymerizable surfactants. In the former case a cream, from which a drug is slowly released, is obtained. On the other hand, creams containing polymerized surfactants can release drugs at a relatively high rate.     

Melting temperature of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water mixtures

The melting temperature (T _m) of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water suspensions has been measured by reflection spectroscopy. A sphere of 110 nm in diameter and 0.041 in monodispersity index is used after purification and deionization processes. Transformation from the body-centered cubic lattice to the face-centered cubic lattice subphases is observed as the suspension temperature rises, which is similar to the purely aqueous suspension of the same sphere. A phase diagram including liquid-like and crystal-like structures is obtained in the presence of ion-exchange resins coexisted. The data ofT _m are analyzed successfully with the theory of Williams, Crandall, and Wojtowicz. The heat of melting decreases by the addition of ethanol or ethylene glycol in the mixtures.     

Effect of pH on colloidal properties of native ovalbumin aqueous systems

The effect of pH on the molecular shape and dispersed state of native ovalbumin molecules in 20 mM phosphate and acetic acid buffer solutions has been studied using small-angle x-ray scattering (SAXS) and a rheological method The degree of association of the OA molecule at the 0.5% colloid system increases slightly with decreasing pH, i.e., 2.10 at pH 7.0, and 2.88 at pH 4.0, and the radius of the OA molecule decreases slightly with decreasing pH, i.e., 24.5 Å at pH 7.0, and 22.0 Å at pH 4.0.The OA colloid shows apparent yield stress and rigidity which are due to a certain ordered arrangement of the molecules. The yield stress and the rigidity increase abruptly at a pH value near to an isoelectric point (ca. pH 4.4). In the dilute system this increment is attributed to the change in the ordered arrangement or in the interparticle interaction, and not to the change in the association state of the OA molecules. The values of the yield stress and the rigidity remain almost constant over a wide concentration range and this feature (an auto-controlled mechanism) is kept over a certain range of pH.     

On the observation of micellar structures by dielectric spectroscopy

Many cationic surfactants form, in the presence of certain organic acids, large supramolecular micellar structures in water. The dielectric response of one such system (cetyl trimethyl ammonium bromide-salicylic acid, CTMAS) has been studied as a function of frequency, concentration and temperature. The results are compared with dynamic mechanical data on the same system, which has been published in the literature.The dielectric response shows that the micelles form a rigid, open network structure, which does not impede ionic transport in the bulk liquid. However, the response also shows the presence of a frequency dispersive barrier capacitance. From the variation of the properties of this capacitance with CTMAS concentration and applied voltage over a range of frequencies, it is deduced that the barrier originates in an ordered micelle structure at each electrode.     

Determination of glass transition temperature,thermal expansion and,shrinkage of epoxy resins

On the basis of measurements of linear thermal expansion of hardened epoxy resins the influence of some modifiers on the thermal expansion of epoxy resin Epidian-5 has been examined. The glass transition temperatures of examined samples were determined.The paper presents also results of the examinations of changes in thermal and cure shrinkage for epoxy resins that occur under the influence of such modifiers as plasticizers and fillers.Five different compositions were examined. A simple and fast measuring method was applied, in which sample elongations vs temperature were determined with a cathetometer. Specific volume changes of liquid resins with temperature were measured with a quartz dilatometer and a cathetometer.     

Characteristics and flow behavior of molten tin-polypropylene blend systems

An experimental study of tin-polypropylene compounds involving melt mixing and melt extrusion and molding over a range of temperatures is described. Problems of coalescence which make continuous mixing impossible above the melting temperature are described. Significant coalescence of the tin also results in extrusion and injection-molding problems. The influence of tin content and melt temperature on shear viscosity and extrusion character is discussed and interpreted. The electrical properties of the compounds are investigated.     

The rheological properties of concentrated cetyltrimethylammonium bromide-salicylic acid solutions in water

Data on the rheological properties of the hexadecyl-trimethylammonium salicylate system (CTAB-SA) in water are reported. Three concentrations were used (0.1, 0.01, and 0.001 M). For the highest concentration, the effect of temperature on the rheology was studied in detail.The rheology of the 0.1 M CTAB-SA solution indicates a very uniform micellar size. By contrast with concentrated polymethyl methycrylate dispersions studied by the author, there was a strong divergence between the viscosity-shear rate and viscosity-frequency data, although the plateau low shear rate and frequency values agreed over a wide range of temperature. This effect could be explained by a shear rate dependent diffusion constant. The large temperature variation of the plateau viscosity and elasticity modulus values could be explained by a combination of micellar number concentration and flexibility changes as the temperature varies.At lower concentrations, the rheological data shows evidence of polydispersity in micellar size. Strong shear thickening and extensional viscosity effects are also evident, probably due to micellar overlap and cluster formation in strong shear fields and the alignment of the very long micelles in elongational flow. The shear thickening effects take some 200 s to relax (0.01 M solution). Recovery of the elasticity after shearing the 0.1 M solution is rapid (a few hundred milliseconds).     

Temperature dependence of the non-Newtonian viscosity of elongated micellar solutions

We report in this work new results of the study on the non-Newtonian viscosity of aqueous micellar solutions of cetyltrimethylammonium bromide (CTAB) in the presence of potassium bromide (KBr), in the concentration range where the elongated micelles overlap. The experiments have been performed as a function of the surfactant concentration, temperature and shear rate by use of a Couette-viscosimeter.In the non-Newtonian range, at relatively low surfactant concentration (0.25 M/l), our results show that the flow curves obtained at different temperatures converge to a single liner curve with a characteristic slope varying with the surfactant concentration. These same data can be superposed on a master curve when appropriate reduced variables are used. The shape of the flow curves obtained at different temperatures for a sufficiently high surfactant concentration is similar to that obtained for monodisperse polymer solutions at different molecular weights. The slope obtained of about –1 is also predicted by Graessley's model in the theory of microviscoelasticity based on the concept of entanglement for polymer solutions. However, at surfactant concentration higher than 0.25 M/l our results show an unusual behavior. Above some critical shear rate it is possible to obtain an increase of the apparent viscosity with temperature. One possible explanation of this effect can be found in the increase of the entanglement with concentration coupled with the temperature and direct now effects on scission and recombination rate of the micelles.     

A reinvestigation of the hypersonic properties and the specific heat capacity of PMMA around the quasi-static glass transition II. High performance caloric investigations

To continue dynamicc _p measurements in the range of smallest temperature rates and non-linear thermal relaxation investigations into the linear range, simultaneousc _p and thermal relaxation measurements were carried out in an adiabatic vacuum calorimeter, using the pulse heating method. The rate-dependentc _p behaviour, known from dynamic measurements, does not continue at small temperature rates. This is confirmed by the relaxation process which is observed. The results suggest an extended interpretation of the glass transition in atactic polymethylmethacrylate (PMMA).     

Studies of polymer solvation by dielectric relaxation spectroscopy II: Polyethylene glycol in methyl pyrrolidone

Frequency domain dielectric spectroscopy (30 MHz to 72 GHz) is utilized to study solvation in polyethylene glycol (PEG) — methyl pyrrolidone (MPy) mixtures over the whole mixture range at 20 °C, in particular with PEG 200. Further pure PEGs (200 to 400) and butyl glycol (in the pure state and in benzene and n-hexane solution) are considered for comparison to facilitate the assessment of PEG relaxational behavior. It turns out that the PEG-MPy mixtures can be described in terms of a simple solvation model which takes into account only the bulk and the solvating solvent state. The solvation number per repeat unit is about 0.85 in the dilute solution limit. It decreases gradually with increasing PEG concentration in accordance with a solvation equilibrium model.     

Microscopic observation of ordered colloids in sedimentation equilibrium and the importance of Debye-screening length. 8. Unsymmetrical ordering and inclusion of anisotropic particles

Unsymmetrical crystal-like ordering of anisotropic-shaped particles are observed directly by a metallurgical microscope in sedimentation equilibrium and in deionized suspensions. The anisotropic colloids are polydispersed gold sols, rectangular tungstic acid, ellipsoidal poly(tetrafluoroethylene)(PTFE), aggregated (dimer, trimer, ...) polystyrene spheres, and bowl-shaped polymers. The distribution of the particles is analyzed by the two-dimensional distance distribution function. The interparticle distance continues to decrease as the initial concentration of the particles increases. Young's elastic modulus for the crystal-like structures is estimated to be 3.1 Pa for PTFE particles. The transformation from the unsymmetrical ordering to the symmetrical (hexagonal) array takes place as the concentration of diffusible ions decreases, which shows that the electrostatic interparticle repulsion and the elongated Debye-screening length around the particles play a key role. Furthermore, a bowl-shaped particle is observed to include a sphere in its cavity. This inclusional association is influenced greatly by the delicate changes in the effective sizes of the host and guest molecules containing the electrical double layers. These results show that electrostatic interparticle repulsion and the elongated Debye-screening length around the particles are essential for the ordering.     

Growth of polyethylene single crystals from the melt: change in lateral habit and regime I–II transition

Using the technique of extraction, single crystals have been obtained from polyethylene fractions isothermally crystallized from the melt at atmospheric pressure. It has been found that the lateral habit of single crystals changes in the vicinity of the transition temperature of growth regime (regime I–II): lenticular shape elongated in the direction of theb axis (type A) in the range of regime I and truncated lozenge with curved edges of {200} and {110} growth faces (type B) in that of regime II. The transition of lateral habit causes a drastic change in the width of {110} growth faces; {110} growth faces are well developed in type B crystals while they cannot be observed and must be very small in type-A crystals. It has been shown that the growth regime of the small {110} growth face of type-A crystals must be in regime I; hence the regime I–II transition can be explained as the result of this change in lateral habit (width of the {110} growth face).     

A monolayer model of the interfacial region of microemulsions

Mixed monolayers of tetradecanol and oleic acid at the water-air interface were studied to provide a static related structure featuring the interface between water and oil of water-dodecane microemulsions.The films of pure components as a function of temperature show a strong area contraction between 25 ° and 30 °C, caused by a change in the head groups hydration. This agrees with similar discontinuities found for some properties of the microemulsion in the same temperature range. At the water-air interface, the composition range of tetradecanol/oleic acid mixtures with the highest thermodynamic stability corresponds to the same stability range of the water-in -dodecane-potassium oleate microemulsions.Adsorption isotherms of tetradecanol and hexanol at the dodecane-water interface were studied to compare the surface behaviour of the two alcohols; the results indicate that the two alcohols have very similar two-dimensional surface phases and adsorption energies.     

The modification of the triple helical structure of gelatin in aqueous solution I. The influence of anionic surfactants,pH-value,and temperature

The modification of the triple helical structure in aqueous gelatin solutions by changing pH and adding alkyl sulphates at 298 K and after rechilling the solution to 283 K was investigated by CD-measurement. At 298 K the triple helical content at the IEP of the gelatin has its maximum value. It is only weakly affected by adding sodium dodecyl sulphate (SDDS) at concentrations <10^–4 M/dm³. The unfolding of the triple helix affected by pH and SDDS is reversible by rechilling the solution. The triple helical content of gelatin solutions decreases at SDDS concentrations higher than 10^–4 M/dm³. In all cases the decrease of the amount of triple helical structure is connected with an increase of the cis-configuration in single chains and leads to chain reversals. At sufficiently high SDDS concentrations-sheets are formed. These changes are thermally irreversible. Sodium decyl sulphate (SDS) has a more minor influence than SDDS except in the range of the c.m.c. of SDS. At sufficiently high SDS concentrations,-turns appear.     

The salt-induced sphere-rod transition of micelles of dodecylpyridinium iodide in aqueous NaI solutions

Static light scattering has been measured on aqueous NaI solutions of dodecylpyridinium iodide (DPI) over NaI concentrations from 0 to 0.05 M. Reduced intensity of scattered light increases with increasing DPI concentration above the critical micelle concentration. The Debye plot is generally a curve with an initially positive slope and with a weakly convex, upward curvature, when the NaI concentration ranges from 0 to 0.005 M. The molecular weight of the spherical micelle of DPI is 28400 in water, and it increases slightly with increasing NaI concentration. The initial slope decreases with increasing NaI concentration and changes from positive to negative across 0.007 M NaI, which is the threshold for the sphere-rod transition and where the micelle has a molecular weight of 34400. At NaI concentrations from 0.01 to 0.05 M, the Debye plot is a curve with an initially negative slope and with a convex, downward curvature. The magnitudes of slope and curvature are larger, and the rodlike micelles of DPI have larger molecular weight and stronger mutual interaction, as the NaI concentration increases. The linear double logarithmic relationship between molecular weight and ionic strength holds for spherical and rodlike micelles, respectively.