Properties of mixed monomolecular films of poly(benzyl-methacrylate) and arachidic acid

Binary mixed monomolecular films of poly(benzyl-methacrylate) and arachidic acid at the water/air interface have been studied with respect to compatibility and stability. The surface pressure — area isotherms indicate compatibility of the two components. However, the miscible state is unstable at high surface pressures. This is demonstrated by the constant pressure relaxation of the mixtures. There is a mechanism of separation and nucleation of the arachidic acid from the film for mixtures with high polymer content at a surface pressure of 30 mN/m. For lower concentrations of polymer in the mixtures and at a surface pressure of 20 mN/m the fatty acid is stabilized by the polymer.     

Dielectric relaxation of rod-like labels in polyisoprene

Rod-like molecules with a strong dipole in the long axis were mixed with synthetic polyisoprene (IR305) in low concentrations (0.1–5 wt%) and measured dielectrically in the frequency range 10^–2–10⁶ Hz and the temperature range –60°–0°C (glass relaxation range). The measurements showed an additional symmetrical relaxation process slower than the glass process by a factor ranging from 10 to 100 times, depending on the length and structure of the label. The label relaxation process was characterized by a narrow distribution of relaxation times and its strong coupling with the segmental motion. For the labels with only a longitudinal dipole moment, no relevant part of the label relaxation was observed in the relaxation frequencies of the glass process; this may be attributed to the parallelism and compactness of the polyisoprene chains. In contrast, the labels with an additional vertical dipole component showed an additional relaxation process superimposed on the glass relaxation with also almost the same distribution of relaxation times. The slow label relaxation could be attributed to a diffusion or rotational diffusion relaxation process through a multistep relaxation mechanism determined by the segmental motion of the matrix.     

Dilatometric study of glass transition kinetics in polyisoprene

From dielectric measurements the thermal dependence and the distribution function of the relaxation times can be determined. In the present contribution we are testing the correspondence between the relaxation times obtained from the dielectric measurement and the dilatometric behavior of the material in the vicinity of the glass transition temperature. The experimental data used for the comparison were obtained for the sample of polyisoprene.     

Hard elastic polypropylene-nature,internal friction,and surface energy

Tensile tests were performed at low temperatures, both in liquid and gaseous nitrogen and also at room temperature, using a series of polypropylene (PP) samples with various technological parameters. Crystalline morphology was also measured for film samples. The results show that liquid nitrogen or solvents can induce materials to create hard elasticity, which strongly supports the bulk-microfibril composite structure proposed by Baer et al., and suggests that the nature of hard elasticity is essentially a craze phenomenon. Three conditions of forming hard elastic structure are discussed. The results from long-time relaxation of hard elastic polypropylene (HEPP) and the improvement of necking of the PP samples in ethanol and water suggest that elastic recovery is reduced by internal friction. The relation between morphology and elasticity is also discussed. The methods of estimating the contribution of surface energy in the recovery process and the increase of surface energy of HEPP during the stretching process are provided. The contribution of surface energy to recovery is about 43% to 66% in the first cycle and after relaxation for 1 h at a maximum of 50% strain. The increased surface energy during stretching is about twice the recovery work done by surface energy.     

Studies of polymer solvation by dielectric relaxation spectroscopy I: polyvinyl pyrrolidone in propylene carbonate,dimethyl sulfoxide and tetramethyl urea

The dielectric relaxation behavior of the title solutions of PVP 40000 is measured in the frequency domain (50 MHz to 36 GHz) at 20 °C. The polymer content of the solutions (up to 0.25 mole fraction of monomer units) is such that it does not yet contribute significantly to dielectric loss. The solvent relaxation shows in all cases a bulk and a slowed down contribution, both characterized by concentration-independent relaxation times. The slow contribution is ascribed to the solvate. Solvation numbers for dilute solutions roughly range between 2 and 4 per PVP repeat unit.     

Analysis of dielectric observations of KCl-charged poly(methyl methacrylate) microcapsules using a two-component model consisting of KCl-permeable and KCl-impermeable capsules

Dielectric measurements were carried out on aqueous suspensions of poly(methyl methacrylate) microcapsules charged with KCl solutions to examine the KCl permeability of the microcapsules. The specimens exhibited three kinds of dielectric relaxation. Two kinds of dielectric relaxation were observed immediately after washing the specimens with distilled water. These overlapped each other when the specimen was left standing in the measuring cell for a long time. Their relaxation frequencies were affected by the KCl concentration of the suspending medium in which the specimen was kept before washing. Another relaxation was observed distinctly when the spepcimens were washed thoroughly with distilled water. Its relaxation frequency was affected by the KCl concentration of the charged solution. These results were explained by assuming that the specimens were mixtures of KCl-permeable and KCl-impermeable capsules. The theoretical analysis procedure was devised in the light of dielectric theory of interfacial polarization to estimate the parameters which characterize the structure of the specimens.     

Chain dynamic parameters for some acrylic polymers

The dielectric relaxation data of Ishida et al. on a number of acrylic polymers are represented in terms of the relaxation function proposed by Havriliak and Negami using the multi-response techniques developed by Havriliak and Watts. Two of the parameters of this function are interpreted in terms of a temperature dependent distribution of relaxation times. In this method of interpretation the breadth of the distribution function is temperature-dependent while the skewness is not. The temperature dependence of the breadth of the distribution function is similar for most of these acrylic polymers.The parameters of the relaxation function are also interpreted in terms of Mansfield's model which represents intra- and inter-molecular interactions in terms of springs and dash pots. Briefly, increasing the side chain length for the methacrylate series increases the inter-molecular relaxation time which may be due to an increase in the entropy of activation for the orientation process. The difference between the one acrylate in this study and the four methacrylates of the series is a reduction in the intra-molecular relaxation time, apparently due to the lack of the alpha methyl group.     

Dielectric relaxation of specially prepared polystyrene terminated with rigid polar groups

Two polystyrenes terminated withp-cyanobenzyl andp-cyanobiphenyl groups (=labels) were prepared and their complex dielectric constants were measured in the glass transition region in the frequency range 10^–2–10⁶ Hz. The glass temperaturesT _g (DSC) were considerably different, 92 and 97.5°C, resp., although their molecular weights were very similar (11 000 and 10 000 g/mol, resp.). Their relaxation behavior showed that the cyano groups relax cooperatively with the polymer segments. The cyanophenyl groups were found to relax with shorter relaxation times than the cyanobiphenyl groups. The measured relaxation strengths showed that there was no association between the dipoles. The relaxation mechanisms of the cyano groups in both labels seemed to be different although the only difference between them was an additional phenyl group in the case of the second label.     

Adsorption of fish oil and poly(vinylbutyral) onto aluminum oxide particles studied by light scattering

The effects of added poly(vinylbutyral) (PVB) and oxidized Menhaden fish oil (O-FO) on dilute suspensions of Al₂O₃ in the azeotropic solvent mixture 73/27 Wt.-% trichloroethylene/ethanol were studied by static (SLS) and dynamic light-scattering (DLS). The DLS correlation function consisted of four terms from: 1) interdiffusion of the two solvents, 2) diffusion of Al₂O₃, 3) diffusion of added O-FO and/or PVB, and 4) an induced velocity of particles through the scattering volume due to laser pressure. The amplitude and relaxation time of all terms could be determined. Addition of PVB to the Al₂O₃ suspension resulted in an increase in particle size corresponding to the adsorption of a monolayer of coils. Addition of O-FO to the Al₂O₃ suspension did not produce a significant increase in particle size, indicating either no adsorption or a compact conformation of O-FO molecules on the Al₂O₃ surface.     

X-ray scattering by black foam films

The x-ray scattering by the three types of black foam films (common black, Newton black, and stratified black films) was experimentally studied. A special device in which flat black films with an area of ca. 2 cm² can be produced was developed and x-ray diffraction patterns were obtained by a vertical diffractometer. The three types of films differ significantly in their x-ray reflections, which proves that they have different structure. For common black films, the comparison of observed and calculated intensities lead to a model, which corresponds to the three-layer model. The Newton black films exhibit diffraction trace with only one highly asymetric peak and there is, as of yet, no unambigous interpretation. The patterns of the stratified black films have several pronounced sharp peaks corresponding to the areas of different films with a given thickness.     

FTIR spectroscopic and NMR studies of hard elastic polypropylene

The variation of amorphous orientation and crystalline regularity of hard elastic polypropylene (HEPP) films during cyclic deformation and stress relaxation processes were studied using a FTIR spectrometer. The result proves entropic elasticity and shows the orientational hysteresis in the amorphous region or within the microfibrils, and also shows that the amorphous orientation increases, but that the crystalline regularity decreases with the increase of extension rate.Three spin-spin relaxation timesT _2f,T _2m, andT _2s and associated mass fractionsF _f,F _m, andF _s of HEPP fibers were measured with a solid echo of NMR method at different elongations and after relaxation or recovery for a long time A new possible interpretation was proposed that, while the microfibrils are formed in HEPP, the medium decay component should be ascribed to inner molecules of the microfibrils, and the slow decay component to the surface molecules of the microfibrils. According to this interpretation, the results implied that subfibrillation is the main process when HEPP is stretched up to 15% strain, and that at above 15% strain thinning and lengthening of the microfibrils become the main process. Thickening of the microfibrils was found in the recovery and relaxation processes.     

Thermotropic gelation of ovalbumin 1. Viscoelastic properties of gels as a function of heating conditions and protein concentration at various pH values

A study has been undertaken of stress relaxation in ovalbumin thermotropic gels with a concentration of 8–20%, depending on time and temperature of heating (respectively, 20–60 min, 70°–110°C), at pH 2.5–10.0. In all instances, the dependence of the initial gel elasticity modulus on heating has a single maximum. Gelation conditions corresponding to this maximum are considered optimal. Optimal gelation time is 30 min, regardless of pH. On the other hand, the optimal heating temperature depends on pH. To the right and left of the isoelectric point of protein (2.5pH<4.0 and 5.5G) of gels on heating conditions, pH and protein concentration (X ₁,X ₂,X ₃,X ₄), as well as on time of relaxation (t) may be generally described asG(X ₁,X ₁,X ₁,X ₁,t)=G _e(X ₁,X ₂,X ₃,X ₄)f(t), whereG _e is the equilibrium value of the elasticity modulus, and f(t) the relaxation function. Thus, a change in the parameters only affects the value of the equilibrium elasticity modulus, and exerts no effect on the relaxation time spectrum. For this reason, all the relaxation curves obtained may be transformed into two normalized relaxation functions:f(t)=f(t)/f(1)=G(X ₁,X ₂,X ₃,X ₄,t)/G(X ₁,X ₂,X ₃,X ₄, 1)Each of these normalized functions corresponds to one of the homologous groups. Rheological similarity of gels in each homologous group evidently points to their structural similarity. Invariance of the gel relaxationproperties with regard to protein concentration, leads to a concentration dependence of the equilibrium modulus at various pH values. These dependences are curvilinear on a double logarithmic scale. The slope of the curve exceeds 2 in the entire concentration interval studied. In other words, the dependences obtained cannot be described by the usual law of squares. On the other hand, they adequately match Hermans theoretical relation for a network formed by random association of identical polyfunctional particles without cyclization. This simple model evidently gives a true picture of the major regularities of thermotropic gelation for ovalbumin. An agreement between this theory and experiment was achieved for a protein concentration ofC ^*=6.0±1.0% at the gel point regardless of pH. Invariance of gelpoint position with regards to pH demands further confirmation.List of symbols T _h,t _h heating temperature and time - T _h ^* ,t _h ^* optimal heating temperature and time - C protein concentration - C ^* protein concentration in gel-point - G relaxation modulus - G _e equilibrium modulus - f(t) relaxation function - t time of relaxation - f(t) normalized relaxation function - fT _A (t), f _B (t) normalized relaxation functions of groups A and B - G ₁ T _h,t _h-reduced modulus - G ₂ T _h,t _h, pH-reduced modulus - G ₃ C-reduced modulus - b ₁ T _h, t_h reduction parameter of modulus - b ₂ pH reduction parameter of modulus - b ₃ C reduction parameter of modulus - W_g gel-fraction     

Influence of crosslinking on mechanical and dielectric properties of nitrile-butadiene-rubber

Several copolymers of acrylonitrile with butadiene (different acrylonitrile content, different molecular weight), uncrosslinked and crosslinked by tetramethylthiuramdisulfide or radiation, are investigated by dynamic mechanical measurements (10^–4 Hz to 100 Hz). The viscoelastic behaviour at very low frequencies is strongly influenced by molecular weight and crosslinking whereas the main relaxation (glass process) remains nearly the same. Stress strain curves (Mullins effect) and some dielectric measurements are also reported.     

Interaction between amphiphiles and water molecules in concentrated bilayer aqueous colloids

Interaction between amphiphiles and water molecules in micelle or bilayer structure has been investigated using aqueous colloids of various amphiphiles through the rheological data and the spin-lattice relaxation timeT ₁ of the proton of water molecule.T ₁ of the water proton has been measured by the inversion recovery method and determined as a single exponential relaxation process.The chemical shift of the water proton is almost independent of the amphiphilic concentration; however, it shifts toward a higher magnetic field with increasing temperature in a way similar to that in pure water and in the amphiphilic aqueous systems. These facts mean that there is no significant difference in the magnetic field environment of the water protons in these systems.The water molecule is not necessarily bound in the fully developed micelle or bilayer (rod-like or lamella) structure which induces the high viscosity or high rigidity of the colloidal system. On the other hand, the water molecule is bound in the micelle colloids of amphoteric amphiphiles or amphiphiles whose molecular assembly creates a relatively strong electrostatic field. The activation entropy of the bound water is negative and this suggests that water molecules assume some ordered structure in the bound state.     

Dielectric relaxation in polymer solids Part 2: Application of the new model to polyurethane systems

Measurements of the complex permittivity of crosslinked polyurethanes at different temperatures in the frequency range 1–10⁵ Hz are discussed with respect to shape of relaxation curves. Using a new model (published in preceding paper) the shape parameters are related to small and large scale interaction.     

Theoretical study of dielectric behavior of microcapsule suspensions with distributed drug release rate

Theoretical consideration is made concerning the dielectric behavior of aqueous suspensions of W/O-type microcapsules containing aqueous electrolyte solutions, especially concerning distribution effects of the electrolyte release rate on the dielectric behavior.It is shown at first that the distribution of the release rate causes electrical conductivity of the capsule interior. Next, it is deduced, in the light of a theory of the interfacial polarization, that the distribution characteristics of the capsule interior's electrical conductivity are closely related to those of the relaxation time for a dielectric relaxation exhibited by the suspensions. Several formulas are derived to describe the relation between the distribution characteristics of the release rate and those of the relaxation time.     

CPS K 221 Model of proton longitudinal magnetic relaxation in hydrated crosslinked poly(methacrylic acid)

Proton longitudinal magnetic relaxation time (T₁) measurements have been made at 30 MHz over a wide range of temperature for crosslinked poly(methacrylic acid), PMA, hydrated with H₂O as well as with D₂O. From the point of view of nuclear magnetic relaxation, PMA hydrogel is a multiregion system in which three proton regions (a, b, c) can be distinguished. Region a is regarded as to be formed by the nonexchangeable polymer protons, region b by the protons of -COOH · H₂O combinations, and region c by the protons of remaining water molecules. Cross relaxation between polymer and water protons and a log normal distribution of correlation times have been assumed to take place. Temperature dependences of the T₁ time for the particular regions have been determined, from which the distribution width parameter, the second moment and the intramolecular proton-proton distance for sorbed water have been calculated.     

Interaction of Na+, K+, Li+ and Ca2+ ions in Tris-HCl buffer substrate with monolayers of phosphatidic acid and homologous phosphatidic acid alkyl esters

The interaction of ions (Na⁺, K⁺, Li⁺, Ca²⁺) with monolayers of phosphatidic acid alkyl esters (alkyl = methyl, ethyl,n-propyl,n-pentyl) were investigated at the air/water interface on Tris-HCl buffer, as well as on the electrolytes containing subphases.Qualitatively it can be stated that there are no considerable interactions between Na⁺ ions in the substrate and the head groups of phosphatidic acid esters in the monolayers. On the whole, the modification of the shape in the /a and v/a isotherms ( ^s = film pressure, v ^s = film potential) of the homologous phosphatidic acid esters as a function of the length of the ester group on the subphase containing NaCl, KCl, and LiCl corresponds to that on Tris-HCl buffer without admixture of electrolytes.On the other hand the strength of interaction between Ca²⁺ ions and the homologous phosphatidic acid esters depends on the length of the ester group. The film-condensing effect of Ca²⁺ ions becomes smaller with increasing length of the ester group.