Kerr Effect of Xanthan/DTAB Aqueous Solutions

The Kerr effect of the Xanthan (charged polyelectrolyte; 113 ppm)/DTAB (surfactant) mixture in aqueous solution was studied. The static Kerr constant (B) and mean relaxation times (τ) values as a function of surfactant concentration (C_DTAB ) were determined. The observed birefringence (Δn) is not a linear function of the electric applied field (E ²). For small E values Δn grows with E ² and at a certain field value the birefringence tends to saturate. The addition of small quantities of DTAB lowers B values with respect to the Kerr constant of Xanthan (113 ppm) aqueous solution. The relaxation time of the mixtures is linearly dependent on the applied field and it decreases when DTAB concentration increases. The importance of the equivalent point is signalled. It is supposed that the initial rigidity of the polyelectrolite decreases because of the surfactant addition. Conductivity (σ) values as a function of surfactant concentration are presented.     

Nonlinear relaxation of stress and birefringence in simple extension of 1,2-polybutadiene

Relaxation of stress and birefringence in simple extension has been studied for two samples of 1,2-polybutadiene with 95% and 88% vinyl content and weight-average molecular weight 1.9 and 2.9 × 10⁵, respectively. The extension ratio, λ, ranged from 1.14 to 2.08, temperatures from 0 to 15°C, and times, reduced to 0°C, up to 3 × 10⁵ sec. The stress-optical coefficient C was negative and positive, respectively, for the two samples, the difference being attributable to opposite signs and very different magnitudes of the contributions of the 1,2 and 1,4 moieties to the birefringence. For each polymer, C was independent of time but increased (algebraically) with temperature. For one polymer a very minor dependence of C on λ was observed. At any instant of time, the dependence of both stress and birefringence on λ could be described by equations of the Mooney–Rivlin form with coefficients C₁,C₂ and B₁,B₂, respectively. At short times the contributions of the C₁ and C₂ terms to the stress and of the B₁ and B₂ terms to the birefringence are roughly equal. With increasing time, C₁ and B₁ decrease gradually while C₂ and B₂ remain constant over several decades in time. Finally, C₂ and B₂ decrease rather rapidly. A tentative interpretation of these phenomena in terms of motions of entanglements is given.     

Dynamic light scattering study of cetyltrimethylammonium bromide aqueous solutions

Cetyltrimethylammonium bromide (CTAB) aqueous solutions are studied by dynamic light scattering method in a wide concentration range covering the first and second critical micelle concentrations (CMC₁ and CMC₂, respectively). Nonmonotonic and ambiguous behavior of diffusion coefficients D with an increase in concentrations above CMC1 is revealed. An increase in the D values in the first decade of CTAB concentration above CMC1 agrees with known published data for aqueous solutions of ionic surfactants. It is shown that an increase in the ionic strength of solution with the addition of KBr leads to a decrease in the positive slope of the dependence of diffusion coefficients on CTAB concentration up to zero at 0.05 M KBr. Two relaxation processes corresponding to large and small D values are simultaneously observed in micellar solutions, beginning with 0.03 M CTAB concentration. The data obtained are compared with published data, as well as with the results of viscosity measurements. The performed analysis indicates that the observed relaxation processes are explained by the coexistence of spherical and nonspherical micelles. It is established that micelles acquire a cylindrical shape at CTAB concentrations ranging from 0.2 to 0.25 M. Hydrodynamic radii and lengths of micelles are calculated.     

Photoviscoelastic behavior of amorphous polymers during transition from the glassy to rubbery state

Tensile stress‐relaxation experiments with simultaneous measurements of Young's relaxation modulus, E, and the strain‐optical coefficient, C_?, were performed on two amorphous polymers—polystyrene (PS) and polycarbonate (PC)—over a wide range of temperatures and times. Master curves of these material functions were obtained via the time‐temperature superposition principle. The value of C_? of PS is positive in the glassy state at low temperature and time; then it relaxes and becomes negative and passes through a minimum in the transition zone from the glassy to rubbery state at an intermediate temperature and time and then monotonically increases with time, approaching zero at a large time. The stress‐optical coefficient of PS is calculated from the value of C_?. It is positive at low temperature and time, decreases, passes through zero, becomes negative with increasing temperature and time in the transition zone from the glassy to rubbery state, and finally reaches a constant large negative value in the rubbery state. In contrast, the value of C_? of PC is always positive being a constant in the glassy state and continuously relaxes to zero at high temperature and time. The value of C_σ of PC is also positive being a constant in the glassy state and increases to a constant value in the rubbery state. The obtained information on the photoelastic behavior of PS and PC is useful for calculating the residual birefringence and stresses in plastic products. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2252–2262, 2001     

Diluent effects on molecular motions and glass transition in polymers. I. Polystyrene–toluene

The effects of diluent on molecular motions and glass transition in the polystyrene–toluene system was studied by means of dielectric, thermal, and NMR measurements. Three dielectric relaxations were observed between 80 and 400°K. On the basis of NMR measurements on solutions in toluene and in deuterated toluene, relaxation processes were assigned to segmental motions of polystyrene, rotations of toluene, and the local motions of polystyrene and toluene in order of appearance from the high-temperature side. The concentration dependence of the relaxation strength and of the activation energy for the primary relaxation (that at the highest temperature) show a step increment at about 50% by weight. The activation plots for the primary process were expressed by the Vogel–Tamman equation. With this equation, the temperatures at which the mean dielectric relaxation time becomes 100 sec is determined. This agrees well with the glass-transition temperature T_g and hence T_g in concentrated solution is expressed by in terms of the parameters A, B, and T₀ of the Vogel–Tamman equation. The values of A and B are, respectively, about 12 and 0.65 and independent of the concentration. The physical meaning of these parameters is discussed.     

Interfacial dilational properties of anionic gemini surfactants with polymethylene spacers

The dilational properties of anionic gemini surfactants alkanediyl-α,ω-bis(m-octylphenoxy sulfonate) (C₈C_mC₈) with polymethylene spacers at the water–air and water–decane interfaces were investigated by oscillating barriers and interfacial tension relaxation methods. The influences of oscillating frequency and bulk concentration on the dilational properties were explored. The experimental results show that the linking spacer plays an important role in the interfacial dilational properties. The moduli pass through one maximum for all three gemini surfactants at both water–air and water–decane interfaces. However, the values of moduli at the water–air interface are obviously higher than those at the water–decane interface because the sublayer formed by spacer chains will be destroyed by the insertion of oil molecules. Moreover, with the increase of spacer length, the surface adsorption film becomes more viscous at high concentration, which can be attributed to the process involving the formation of the sublayer. On the other hand, the spacers of the adsorbed C₈C₆C₈ molecules will extend into the oil phase when the interface is compressed. As a result, the interfacial film becomes more elastic with the increase of spacer length at high concentration. The experimental results obtained by the interfacial tension relaxation measurements are in accord with those obtained by the oscillating barriers method.     

Solution behavior of random copolymers of styrene with sodium-2-acrylamido-2-methylpropane sulfonate

The nonaqueous solution behavior of random copolymers of styrene (ST) with sodium-2-acrylamido-2-methylpropane sulfonate (Na-AMPS) [poly(ST-Na-AMPS)] has been investigated using the transient electric birefringence (TEB) technique. The copolymers with varying high sulfonate contents (about 30–70 mol%), bridging the gap between conventional ionomers and classical polyelectrolytes, were dissolved in the solvent methylformamide (MFA) with a high permittivity ? of ca. 190. The solutions showed a negative birefringence at electric field strength E of the order of kV/cm. A typical Kerr effect was observed at low polymer concentrations C of ca. 10^?3g/mL and electric field strengths of the order of kV/cm. However, the detailed, TEB studies demonstrated different behavior at two concentration regimes in dilute solution. At a low concentration regime (e.g., C ≤ 1 × 10^?3g/mL for the copolymer with a 66.7 mol % sulfonate content) where the reduced viscosity exhibited a pronounced polyelectrolyte effect, the birefringence signal pattern showed a maximum before reaching a steady value. Additionally, during the rise at an applied electric field strength beyond a threshold value, it was observed that the nonexponential field-free decay was slower than the single exponential field-induced rise. The observed anomalous behavior was similar to those of a polyelectrolyte [sodium poly (styrene sulfonate)] in aqueous solution and might be attributed to the perturbation of the molecular shape by the applied electric field. At the higher concentration regime (e.g., C ≥ 4 × 10^?3g/mL for the same copolymer with a 66.7 mol % sulfonate content) where the polyelectrolyte effects started to diminish as indicated by the viscosity study, the birefringence shape showed no variation with an increased electric field strength and the field-free decay turned out to be faster than the single exponential rise. The dissociation of ionic aggregates was tentatively interpreted to be responsible for this observation. It seems that by simply varying the polymer concentration, poly (ST-Na-AMPS) could behave either as a polyelectrolyte or as an ionomer in a single polar organic solvent.     

FLUORESCENCE PROBE STUDIES ON THE SECOND CRITICAL MICELLE CONCENTRATION OF SEVERAL KINDS OF SURFACTANTS

The fluorescence intenstiy ratios (F₂/F₁) of excimer (F₂) to monomer (F₁) of probe (pyrene) were measured as a function of the concentration of the surfactant in several systems, which consist of sodium hexadecyl sulfonate (C₁₆As)-anionic surfactant, cetyltrimethylammonium bromide (CTAB)-cationic surfactant and pentaoxyethylene decyl ether (C₁₀E₅)-nonionic surfactant. The second CMC values were obtained according to F₂/F₁ ~ surfactant concentration curve break. In addition, we also studied the variation of second CMC vs NaCl concentration. It was found that the second CMC values of C₁₆A₅ and CTAB decreased with the increase of NaCl concentration. But the present of NaCl had no influence on the second CMC value of C₁₀E₅. Results showed that sphere-shaped micelles turn into rod-like micelle at the second CMC. The results were interpreted in terms of diffusion of pyrene molecules and the distribution of pyrene among micelles.     

Effects of polymer chain disentanglement on NMR properties. II. 13C magnetic relaxation in polystyrene

The transverse magnetic relaxation of ¹³C_α nuclei has been studied in concentrated solutions of polystyrene. The magnetic relaxation rate was measured as a function of molecular weight at several temperatures (313,318, and 323 K) and at several concentrations (0.53, 0.43, and 0.34 g/cm³). The spin-system response of these nuclei in natural abundance exhibits a characteristic evolution from pseudosolid properties to liquidlike one, induced by decreasing the molecular weight of polymer molecules. This evolution is analogous to that already observed in protons attached to polyisobutylene or polydimethylsiloxane chains; it is assumed to be induced by an increase of the disentanglement rate of polymer chains. The spin-system response may be considered as reflecting single-chain magnetic properties, because of the low concentration of ¹³CC_α nuclei, although all chains are in dynamic interaction with one another. The NMR disentanglement transition is interpreted in terms of a two-step motional averaging effect involving submolecules. A numerical analysis of NMR properties is given using a model of polymer chain relaxation based on a multiple-mode relaxation process, characterized by (i)a terminal relaxation time τ^v₁ depending upon M³, the molecular weight, and approximately proportional to the polymer concentration C (like the reptation time); (ii)a relaxation-time spectrum analogous to a Rouse spectrum; (iii)a terminal relaxation time τ^v₁ = 2.5 × 10^?2s for M = 2.5 × 10⁵, C = 0.53 g/cm³ in carbon tetrachloride at 313 K.     

Refractometry of lyotropic mesophase systems: Ethyl cellulose/m-cresol and ethyl cellulose/acetic acid

An Abbé refractometer with a rotatable polarizer mounted on the eyepiece is used for determining the two principal refractive indices of birefringent concentrated solutions of ethyl cellulose in m-cresol and in acetic acid. At a certain concentration, birefringence appears for both systems, and the concentration agrees with that for the onset of iridescence (here defined as the critical concentration C_a for formation of the liquid-crystalline phase). The birefringence of concentrated solutions depends strongly on concentration and temperature and can be generalized by a master curve. The refractive index increments for both systems are almost independent of temperature at high concentrations.     

Aggregation behaviors of amine-oxide gemini surfactants

The micellar aggregation of a series of gemini surfactants [N, N’-dimethyl-N, N’-bis(2-alkylamideethyl)-ethylenediamine oxide (alkyl?=?C₁₁H₂₃, C₁₃H₂₇, C₁₅H₃₁)] in aqueous media has been investigated. The results show that there is an excellent agreement among the critical micelle concentration (CMC) values obtained by surface tension and steady-state fluorescence methods. Because of the occurrence of self-coiling or the formation of pre-micellization, the CMC values, the I₁/I₃ values, and the micelle aggregation numbers (N_agg) at CMC (N_m) increase with the hydrophobic alkyl chain length increasing. Besides, vesicles are observed above the CMC for all these surfactants.     

Electro-optics of solutions of biopolymers and their complexes

The review summarizes the results of electric-birefringence studies of the molecular properties of biopolymers and their complexes. The application of alternating electric fields makes it possible to study the kinetics of orientation of DNA, RNA, and polypeptide molecules in diluted solutions. An analysis of molecular-mass dependences of relaxation times of biopolymer molecules in terms of the rotational friction theory is used to determine the equilibrium rigidity of macromolecules characterized by Kuhn segment length A. For DNA molecules in buffer solutions with a low ionic strength, the value of A derived from electro-optical measurements is 114 nm. The high sensitivity of electric birefringence to changes in the secondary and tertiary structures of biopolymers ensures its use for the analysis of sequence curvature in short fragments of DNA and for investigation of transitions between different tertiary structures of RNA. The study of electro-optical birefringence in solutions of complexes of DNA and polypeptides with oppositely charged ions of surfactants makes it possible to gain insight into their conformational properties in organic solvents. The stoichiometric complexes of DNA in chloroform occur in the compact globular state, whereas the conformation of complexes formed by various polypeptides depends on their composition and may vary from rodlike to coiled. Electric birefringence in solutions of biopolymer complexes is associated with the orientation of molecules that is due to the external-field-induced dipole moment that appears as a result of a small displacement of ions along the contour of polyion chains. The time of reaching the induced dipole moment is equal to or greater than the time of orientational relaxation of the complex as a whole.     

Diffusion in a multicomponent inhomogeneous system with moving boundaries. I. Swelling at constant volume

A medium B contains a substance C which can diffuse. This mixture of B and C is brought into contact with a medium A which itself can diffuse into B. Now C diffuses through a swollen layer of A and B into A. The present study examines mathematically this process which, among other things, could serve as a model for migration in a system consisting of plastic packaging (polymer plus an additive) and the contents of the package. It is assumed that medium A (contents) with a constant diffusion coefficient diffuses into medium B (plastics) and that the diffusion of substance C (additive) in the pure B and into A can also be described by constant diffusion coefficients. The diffusion coefficient of substance C in the zone of mixed A and B is taken to be dependent on the concentration of A in B. Partition coefficients are assumed to exist at all interfaces between the media. The general equations of this coupled diffusion process are solved explicitly. The solutions are discussed and illustrated by several special cases. Furthermore, the total amount of C in A is calculated as a function of the diffusion coefficients of the partition coefficients of time, and of the concentration of A in B.     

The effect of locations of triple bond at terphenyl skeleton on the properties of isothiocyanate liquid crystals

Three series of new tolanyl benzene isothiocyanate liquid crystals A, B and C were synthesised with lateral fluorine substituent at different positions and 3,5-difluoro terminal groups. Series D and compound E4 with carbon–carbon triple bond connected with the isothiocyanated benzene were also prepared as reference. Their structures were confirmed using infrared spectrometry, nuclear magnetic resonance and mass spectrometry. The mesomorphic properties, birefringence, dielectric anisotropy and miscibility of these compounds were investigated. Series A exhibits higher clearing points than that of the corresponding compounds D. Series B displays the lowest melting points, the broadest nematic phase temperature range and no smectic phase with increase of the carbon number of alkyl chain. Lateral fluorine in the position of Y (series C) results in an increase of smectic phase. The birefringence (~0.454–0.490) of series A is almost the same as that of the corresponding reference compounds D, while series B shows a decrease of Δn about 0.05 compared with compounds D. For comparison, mixtures formulated by A and B exhibit higher clearing points and better low temperature stability than those of the mixtures based compounds D in the same fraction.     

Mechanical relaxations and moduli of oriented nylon 66 and nylon 6

The mechanical relaxations of dry and wet nylon 66 and nylon 6 with draw ratios λ = 1–3 have been studied from ?180 to 160°C and in the frequency range of 1 Hz to 10 MHz. The five independent elastic moduli C_11, C_12, C_13, C_33, and C₄₄ have also been determined by an ultrasonic method at 10 MHz. Wide-angle x-ray diffraction and birefringence measurements reveal that the crystalline orientation rises sharply at low λ and becomes saturated near λ = 3; the amorphous orientation function increases continuously, reaching values of 0.3–0.5 at λ = 3. The alignment of molecular chains and the presence of taut tie molecules in the amorphous regions lead to a lowering of segmental mobility, thereby reducing the magnitude and increasing the peak temperature and activation energy of the α relaxation. Water absorption weakens the interchain bonding and so gives rise to effects opposite to those of drawing. At low temperature, the development of mechanical anisotropy is largely determined by the overall chain orientation, with the c-shear mechanism contributing a small additional effect. However, above the α relaxation, where the amorphous region is rubbery, the stiffening effect of taut tie molecules becomes dominant and leads to increases in all moduli.     

Untersuchung iiber die Wechselwirkung Polymere-Tenside

Zusammenfassung Es wurde der Einfluß von Polyvinylpyrrolidon (PVP) auf die kritische Mizellenbildungskonzentration (CMC) der Natriumsalze gesättigter und ungesättigterC ₁₆- undC ₁₈-Fettsäuren studiert. Die Oberflachenspannungskurven wiesen die Knickpunktet ₁ undt ₂ auf, die dem Adsorptionsbeginn bzw. der Polymersättigung an Tensidionen entsprechen. Wahrendt ₁ nur von der CMC des Tensids abhangt, istt ₂ an die CMC des Tensids und an die Polymerkonzentration gebunden. Die Gegenwart von Polymer-Tensid-Adsorptionskomplexen in Lösung verschiebt die CMC gegen höhere Konzentrationen, die dert ₂-Konzentration entsprechen. Die Polymer-Tensid-Wechselwirkung nimmt mit steigender PVP-Konzentration (im Konzentrationsbereich 0,25–0,50%) und mit der Verstarkung des hydrophoben Characters der Tenside in der Reihe:Stearat > Palmitat > Elaidinat > Oleat zu. Die Leitfahigkeitskurven zeigen keine Übergangspunkte.

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Summary The influence of polyvinylpyrrolidone (PVP) on the critical micellar concentration (CMC) of the sodium salts of saturated and unsaturatedC ₁₆ andC ₁₈ carboxylic acids was investigated. The surface tension curves displayed transition pointst ₁ andt ₂ corresponding to the adsorption outset and to the saturation of the polymer in tensid ions, respectively. Whilet ₁ only depends on the CMC of the tensid,t ₂ depends both on the CMC of the tensid and on the polymer concentration. The presence in solution polymer-tensid adsorption complexes shifts the CMC towards higher concentrations, corresponding to thet ₂ concentration. The polymer-tensid interaction increases with the increasing PVP concentration (in the concentration range 0.25–0.50%) and with the strengthening of the hydrophobic character of the tensids, in the order: stearate > palmitate > elaidinate > oleate. Conductivity curves did not display the two transition points.

     

Rheological properties of carboxymethyl cellulose (CMC) solutions

In this study, we investigated the way of predicting two critical concentrations of sodium carboxymethyl cellulose (CMC) solutions using simple experimental procedures with a rotational rheometer. It was found that, above a critical shear rate, all CMC solutions (0.2 to 7 wt.%) exhibit shear-thinning behavior and the flow curves could be described by the Cross model. A first critical CMC concentration c*, transition to semidilute network solution, was determined using the following methods (1) study of the flow curve shapes, (2) Cross model parameters, (3) plot of the specific viscosity vs the overlap parameter, and (4) empirical structure–properties relationships. Furthermore, both creep and frequency-sweep measurements showed that the solutions behaved as viscoelastic materials above a second critical CMC concentration c** (transition to concentrated solution). The characterization of CMC solutions was completed with a time-dependent viscosity study that showed that the CMC solutions exhibited strong thixotropic behavior, especially at the highest CMC concentrations.     

Dynamic x-ray diffraction studies of high-density polyethylene

Dynamic x-ray diffraction is conducted to explore the structural origin of the α and β mechanical dispersions of a melt-crystallized high-density polyethylene. It is shown that the real component of the strain orientation coefficient for the crystal c axis C decreases with increasing frequency at a rate which decreases with decreasing temperature. Values of C for the c axis are positive, C for the a axis negative, and C for the b axis close to zero, suggesting that the predominant relaxation process is crystal rotation about the b axis. The activation energy found from Arrhenius plots of C corresponds to that of the α₁ mechanical dispersion. The dynamic birefringence in this region is dominated by the contribution from crystal orientation changes. At low temperatures, the imaginary component KC of the strain-optical coefficient of the crystal phase approaches zero, while KC of the amorphous phase exhibits a somewhat broad dispersion peak corresponding to the β birefringence dispersion. This suggests that the principal contribution to the β birefringence dispersion arises from the amorphous phase, probably owing to the amorphous orientation process. Contrary to the case of low-density polyethylene, the dynamic crystal lattice deformation and compliance functions reveal distinct frequency dispersions corresponding to the α₁ and α₂ mechanical processes. The α₁ lattice dispersion is thought to be associated with the α₁ crystal orientation dispersion, while the α₂ lattice dispersion is believed to be the inherent one arising from the onset of intracrystalline chain motions.     

Interfacial Properties of Aqueous Nonionic Fluorocarbon Surfactant Solutions

The equilibrium, dynamic surface tensions, and surface dilatational elasticity of aqueous solutions of nonionic fluorocarbon surfactant are reported. The critical micellar concentration, CMC (0.023 mM) and equilibrium surface tension (24.6 m N . m^?1) at CMC were measured by Wilhelmy plate method for aqueous solution of C₈F₁₇SO₂N(C₃H₇)(C₂H₄O)_nH (n=20), abbreviated as EF122A. The surface tension decay is slower for C₈F₁₇SO₂N(C₃H₇)(C₂H₄O)_nH (n=10) system, abbreviated as EF122B compared to the EF122A system over short time region, which indicates the slow transport of the surfactant molecules to the surface. The relaxation time for surface tension decay is estimated by fitting a series of exponentials to the dynamic surface tension data and it decreases with temperature for EF122A. Slow exchange of monomers between bulk and interface is reflected in the high elasticity value of the air‐liquid interface for EF122B compared with EF122A within measured frequency window (0.125–1.25 Hz).