New organosols of ZnS and HgS in N,N-dimethylformamide and dimethyl sulfoxide. Use in the preparation of semiconductive polymer-metal sulfide composite films

Organosols of ZnS and HgS in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were prepared by reaction of Zn and Hg salts with H₂S. ZnS in the DMF organosol has a particle size of about 300 Å, determined by an argon laser scattering technique. The form of HgS in the organosols varies with temperature, concentration of HgS, and type of solvent;-HgS in a DMF organosol is converted into-HgS at –30 °C or above. Poly(acrylonitrile)-ZnS or -HgS composite films prepared from organosols are semiconductive, and the electrical conductivity of the film increases by a factor of 10²–10³ on exposure to moisture or alcohol vapour. Poly(acrylonitrile)--HgS composite films, prepared from heated-HgS, show electrical conductivity of a range of 10^–1–10^–2 S cm^–1 and a large electron mobility.     

Rigid-rod polymers with flexible side chains

Modeling studies were performed for a rigid-rod polyester with hexadecyloxy side chains (n=16) in order to simulate x-ray scattering curves in the medium angle scattering region (s=4 sin / from 0.2 Å^–1 to 2.2 Å^=t–1). The experimental ones were taken from a material obtained by cooling to room temeperature from the smectic mesophase at 150°C. The wide-angle x-ray diffractograms were calculated for given conformations and molecular arrangements using Debye's equation. The theoretical result thus obtained for a great variety of possible packing models and structures was compared to the experimental result. The size of the effective scattering region is found to be 61×18×52=6×10⁴ ų and consists of approximately five layers, each of which is composed of two rigid rods and 20 side chains. The planes form by the rigid rods, together with the side chains, have a distance of 3.6 Å, the distance between the rods being 26 Å. As the main result, it was found that the side chains form regions with a denser ordering (clustering). The interchain distance for side chains decreases in the regions from 5.3 Å to 4.8 Å.     

The effect of particle concentration on zeta potential in extremely dilute solutions

The electroporetic mobility of hexadecane particles in water and in very dilute CTAB solutions was measured. The technique of microelectrophoresis was applied. Zeta potential was calculated according to the Hückel formula, applying Henry's correction factors. Electrokinetic charge density was calculated according to the formula used by Delgado et al., and previously discovered empiricaly by Loeb et al. and derived mathematicaly by Ohshima et al. It was found that the particle concentration in emulsion limits their charge in solutions of very low ion concentration (10^–7:10^–6 M), because the greater the particle concentration, the smaller the extent of the ions adsorbed at the surface of one particle. The zeta potential was found to be independent of particle concentration if the ratio of the number of bulk ions to particle number is not lower than 1.6×10⁶. This ratio depends on particle size, and the value 1.6×10⁶ relates to particles of diameter 1.6 m.     

Electrically conducting,thermally stable,and mechanically strong CuS-poly(parabanic acid) composite films and their shielding effect of electromagnetic wave

Poly(parabanic acid)-CuS composite film (wt-% of CuS=20–50) prepared by using organosol of CuS (=1500 Å) showed electrical conductivity of 0.1–70 S cm^–1, high thermal stability up to 250°C, high mechanical strength (breaking stress=7.0–12 × 10⁷ Pa), and good shielding effect of electromagnetic wave.     

Scattering from concentration fluctuations in polymer blends: A monte carlo investigation

The collective scattering function S_coll( ), which describes light (neutron-, x-ray) scattering under wavevector , is obtained from Monte Carlo simulations for a symmetrical polymer mixture. The polymers are modelled by self-avoiding walks ofN _A=N_B=N steps on a simple cubic lattice, where a fraction _V of sites is left vacant, and an attractive energy occurs if two neighboring sites are taken by the same kind of monomer. Spinodal curves are estimated from linear extrapolation of S _coll ^–1 (0) vs./k _B T, whereT is the temperature. Also the single chain structure factor is obtained and the de Gennes random phase approximation (RPA) can thus be tested. Unexpectedly, strong deviations are found if one species is very dilute. The estimation of an effective Flory-Huggins-parameter from scattering data is also discussed.Contributed paper delivered at the Tagung der Deutschen Physikalischen Gesellschaft, Fachausschuß Polymerphysik, Hamburg, March 14–16, 1987.     

An estimation of the surface ionization constant of oleic acid in aqueous sodium chloride solution

The zeta potential () measurements and the site binding theory were utilized for calculations of the parameters of the electrical double layer (edl), ionization, and complexation constants for oleic acid-aqueous sodium chloride solution interface. Assuming that is equal to the diffuse layer potential ( _d ) of the edl, the charge of the diffuse part of the edl was calculated from the Gouy-Chapman equation. The intrinsic ionizaiton constant was then determined by an extrapolation method to be . Subsequently, the surface potential ( ₀) was calculated, and it was found that ₀ changes by 50 mV per pH unit (50 mV/pH) or 42.5 mV/pH for 10^–3 and 10^–2 M NaCl, respectively. For further calculations, the integral capacity of the outer zone of the compact part of the edl was assumed to be for both ionic strengths. It was established that the intrinsic complexation constant for the binding of Na⁺ ions with the surface of oleic acid ispK _Na ^int = 2.9±0.5 if the integral capacity of the inner zone of the compact edl (K ₁) is 80 for 10^–3 M NaCl, but 280 for 10^–2 M NaCl. The use of the sameK ₁ value for both ionic strengths gives a differentpK _Na ^int for different NaCl concentrations, and also provides unrealistic surface charge ( _o ) values greaterfor 10^–3 M NaCl than for 10^–2 M NaCl, at the same pH of the solution.     

Secondary structural changes of chymotrypsinogen A,alpha-chymotrypsin,and the isolated polypeptides Cys1-Leu13, Ile16-Tyr146, and Ala149-Asn245 in sodium dodecyl sulfate,urea and guanidine hydrochloride

Secondary structural changes of chymotrypsinogen A,-chymotrypsin, and their isolated polypeptides Cys¹-Leu¹³, Ile¹⁶-Tyr¹⁴⁶, and Ala¹⁴⁹-Asn²⁴⁵were examined in aqueous solutions of sodium dodecyl sulfate (SDS), urea, and guanidine hydrochloride (residue numbers from chymotrypsinogen). After the fragmentation by the cleavage of disulfide bridges in-chymotrypsin, the helical structure was formed in the isolated polypeptide 16–146 where the helical segments do not exist in the protein state. The polypeptide 149–245, where the helical segments of the parent protein are originally located, contained no helices. The polypeptide 1–13 was almost disordered. The three polypeptides, chymotrypsinogen,-chymotrypsin and the polypeptide 16–146, clearly showed differences in the stabilities of helical structures in solutions of urea and guanidine hydrochloride. The addition of SDS accelerated the formation of helical structures in each polypeptide except for 1–13.     

Mass,size and shape of micelles formed in aqueous solutions of ethoxylated nonyl-phenols

The study was extended to analysis of mass, size and conformation of micelles formed in aqueous solutions of ethoxylated nonyl phenols. The results obtained by ultracentrifugal technique between 293 and 323 K have proved that the slightly ethoxylated nonyl phenols form micelles with high molecular mass and larger size at constant temperature, while the increasing length of the ethylene oxide chain favours formation of micelles of smaller molecular mass and size. The transformation of conformation from oblate to spherical shapes ensues with increasing temperature at constant ethoxy number or with ethoxylation at constant temperature. The second virial coefficient decreases with increasing temperature and decreasing ethoxy number. In accordance with the earlier conclucions, the change of the second virial coefficient relates to enhanced variation of monomer solubility, stabilization of micelle structure and increased deviation from ideal behaviour of a given micellar system.Symbols a major axis of micelle, Å - a _m attractivity factor, cm³ erg molecule² - b minor axis of micelle, Å - c concentration, g dm^–3 - c _b equilibrium concentration at the bottom of the cell, g dm^–3 - c _m equilibrium concentration at the meniscus of the cell, g dm^–3 - c _o initial concentration in the cell, g dm^–3 - c _M critical micellization concentration, mol dm^–3 - e eccentricity - f _IS Isihara-constant - f/f _o frictional ratio of micelle - amount of water in micelle per ethoxy group, mol H₂O/mol EO - n aggregation number, monomer micelle^–1 - n _EO number of ethoxy groups - r distance of Schlieren peak from the axis, cm - r _b distance of cell bottom from the axis, cm - r _m distance of cell meniscus from the axis, cm - R _h equivalent hydrodynamic radius of micelle, Å - s _t sedimentation coefficient, s - reduced sedimentation coefficient, s - reduced limiting sedimentation coefficient, s - ¯v _t volume of micelle, cm³ micelle^–1 - partial specific volume of solute, cm³g^–1 - partial specific volume of solute reduced to 293 K, cm³ g^–1 - B _a, B_e constants, cm³ mol g^–2 - B ₂ second virial coefficient, cm³ mol g^–2 - M _m ^a mass average apparent molecular mass of micelle, g mol^–1 - M _m mass average molecular mass of micelle corrected withB ₂, g mol^–1 - M _m ^cM mass average molecular mass of micelle belonging toc _M, g mol^–1 - M ¹ mass average molecular mass of monomer, gmol^–1 - N _A the Avogadro's number, molecule mol^–1 - R universal gas constant, erg mol^–1 K^–1 - T temperature, K - _t ^o dynamic viscosity of solvent atT temperature, g cm^–1 s^–1 - dynamic viscosity of solvent at 293 K, g cm^–1 s^–1 - _t density of solution atT temperature, g cm^–3 - _t ^o density of solvent atT temperature, g cm^–3 - density of solvent at 293 K, g cm^–3 - angular velocity, rad s^–1 - time, s     

Crystal structure of ionic and non-ionic surfactants based on polyoxyethylenated dodecanol: A13C-CP-MAS-NMR and x-ray investigation

Crystal structure of monodisperse non-ionic surfactants having the general formula C₁₂H₂₅O–(CH₂–CH₂–O)_nH (C₁₂E_n),n=7,9, 10, 15, 16 and ionic derivatives, C₁₂H₂₅–O–(CH₂–CH₂–O)_n–CH₂COONa (C₁₂E_nC),n=3,4,5,6,7,9, 12 has been investigated by¹³C-CP-MAS-NMR and x-ray diffraction. A structural model, in which aliphatic and polyether segments are segregated in bilayers stacking parallel to the elongation direction of the molecules, fits the experimental data for both series. The experimental values of the repeat distance along the stacking directiond(001) are linearly dependent onn and the slope is nearly equal to twice the repeat distance of7/2 helix conformation, which is typical for crystalline polyethyleneoxide. The values ofd(001) agree very well with the values expected for the C₁₂ segment in a planar zig-zag conformation, which is tilted with respect to the polyerther segment (7/2 helix conformation) in such a way that both the aliphatic and the polyether regions adopt the mass density of the corresponding crystalline compound. Two additional phases have been detected for C₁₂E_nC. One of them is probably characterized by the planar zig-zag conformation of the polyether chain. The meader model, previously proposed in the literature for surfactants containing polyethylene oxide segments is inconsistent with the obtained experimental data.     

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.     

Dielectric properties of cleaned and monodisperse polystyrene latexes in microwaves

The dielectric behavior (, ) of three well-cleaned monodisperse polystyrene latexes having the same particle size and the same number of chemically-bound surface groups has been studied at a fixed microwave frequency (9.4 GHz), as a function of temperature and surface group (SO ₄ ^– , COO^–, OH).A large dielectric relaxation was observed in the sulfate-stabilized latex, which has the most polar surface end-group. The anomalous behavior in the thermal dependence of the hydroxyl and carboxyl-stabilized latexes (the OH latex being more pronounced than the COO^– latex) may originate from differences in the experimental conditions used for the preparation of such polymer colloids, or due to the presence of ionic species.On the basis of various dielectric models, the apparent volume fractions of the latexes were calculated. The amount of bound water around the latex particle was quantitatively correlated to the polarity of surface end-group (SO ₄ ^– > COO^– > OH). The differences between the calculated and actual values were not only a reflection of the thickness of vicinal water, but could also be indicative of the presence of oligomeric species in the suspension's medium (serum) of the latex. The permittivities of hydrated particle and of bound water were obtained with a non-linear iterative procedure.     

Determination of the regime in the reverse wilson chamber at critical supersaturation measurements

The pressure in the Reverse Wilson Chamber (RWC) was directly measured at different rates of compression of the gas mixture. It was shown that at compression time in the range from 0.06 to 0.3 s an intermediate, between adiabatic and isothermal, process took place in the chamber. To obtain the relative pressure increase P _m /P _at from the values of the relative gas compression V/V, a calibration of the experimental set-up was carried out. The calibration showed that the values of critical supersaturationSc for water condensation on hexadecane, estimated for intermediate regime of the gas compression, were reduced with respect to the values calculated when the adiabatic regime was assumed. This fact confirmed the conclusions made earlier [1–3] that the classical theory was not applicable in this case of heterogeneous phase formation and that the line tension < 0 should be taken into account. Moreover, in an atmosphere of very pure argon (instead of room air [1–3]) the critical supersaturation turned out to be independent of the initial state of undersaturationS _o . The more accurate values obtained for condensation of water on hexadecane were: lnS _c =0.204 (instead of the maximum value obtained earlier: lnS _c =0.26) and=–1.9×10^–5 dyne (instead of=–1.5×10^–5 dyne).     

Characterization of water-soluble,cationic polyelectrolytes as exemplified by poly(acrylamide-co-trimethylammoniumethylethacryate chloride) and the establishment of structure-property relationships

The cationic copolymerization products of poly (acrylamide-co-trimethylammoniumethylmethacrylate chloride (PTMAC) having cationic monomer percentages of 8%, 25%, and 50% as well as the cationic homopolymer, were characterized with respect to their molecular dimensions. The light-scattering and viscometric measurements were carried out for molecular weights ranging from 200 000 to 12 800 000 g/mol in 1 M NaCl solution at 25°C. It was possible to establish a relationship between the molecular weight and the two parameters: intrinsic viscosity and radius of gyration, for all four polymers.Rheological investigations of the flow properties in 1 M NaCl solution were also carried out using the polymer with a cationic monomer of 50% (PTMAC 50). Structure-property relationships were formulated which made it possible to describe and predict the shear viscosity, both in the zero-shear region (Newtonian region) and in the shear-dependent region (non-Newtonian region) as a function of the polymer concentration, the molecular weight, and shear rate.Abbreviations a exponent of the []-M relationship - A ₂ 2^nd virial coefficient/mol·cm³·g^–2 - AAm acrylamide - b slope of the flow-curve in the shear-rate dependent region - c concentration/g·cm^–3 - dn/dc refractive index increment/cm³·g^–1 - f function - K constant of the []-M relationship/cm³·g^t-1 - m _c proportion of cationic monomers/mol % - M molecular weight/g·mol^–1 - M _w weight-average molecular weight/g·mol^–1 - M _n number-average molecular weight/g·mol^–1 - NaCL sodium chloride - PAAm polyacrylamide - PS polystyrene - PTMAC poly(acrylamide-co-trimethylammoniumethylme thacrylate chloride) - R_G ^20.5 radius of gyration/nm - TMAC trimethylammoniumethylmethacrylate chloride - shear rate/s^–1 - critical shear rate/s^–1 - viscosity/Pa·s - 0 zero-shear viscosity/Pa·s - _s solvent viscosity/Pa·s - _sp specific viscosity - [] intrinsic viscosity/cm³·g^–1 - relaxation time/s     

Electrical properties of poly(bis(β-phenoxyethoxy)phosphazene) and its complexes

Electrical and dielectrical properties of poly(bis(-phenoxyethoxy)phosphazene) (I) and its complexes with various content ratios of AgSO₃CF₃ to monomeric unit (0.25/1 (II) and 0.5/1 (III) in molar ratio) were investigated.Dc conductivity of respective samples at 18 °C were 6.1×10^–12, 4.4×10^–9, and 7.1×10^–8 S/m.Dc conduction was considered to be due to ion hopping. Charge mobility ranged from 3×10^–12 to 6× 10^–11 m²/Vs depending on the applied field in sample II. In sample I, a tan peak was found which can be ascribed to molecular relaxation of main chains. The peak vanished upon introducing AgSO₃ CF₃. Temperature dependence of total conductivity ( _T ) measured byac method in the temperature range between –150 °C and 50 °C showed several peaks at the temperatures corresponding to the peak temperatures of tan. Total conductivities of respective samples at 100 kHz were 4.9×10^–7 (69 °C), 1.7×10^–4 (45 °C), and 1.5×10^–4(40°C)S/m.     

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.     

Comparison of galactomannan crosslinking with organotitanates and borates

Water-soluble polymers crosslinked with metal ions form stable gels that are used in oil and gas production processes. We present an investigation of the chemistry of the binding between guar galactomannans and both borates and titanates using NMR and dynamic light scattering. The two monosaccharides comprising guar — methyl--D-galactopyranoside and methyl--D-mannopyranoside — have been studied as model compounds. High resolution¹³C NMR detected complexation of the sugars with borate but displayed no sign of complexation with either of the two titanates even at high titanate concentrations. Dynamic light scattering studies demonstrated the existence of colloidal titanium dioxide particles for both titanate crosslinkers. The loss of free titanium to the colloidal particles reduces the concentration of titanium crosslinking sites to below the detectable limits of NMR. The role of colloidal titanium dioxide colloids in these crosslinking reactions has not been reported previously. Data are presented following the growth of these particles with time as a function of pH and salt concentration. The observed particle growth kinetics explains the observed sensitivity of the guar gelation process to these variables.     

Small-angle neutron scattering on shear-induced micellar structures

Small-angle neutron scattering (SANS) experiments on sheared aqueous surfactant solutions of tetradecyltrimethylammoniumsalicylate (TTMA-Sal) are reported. A5-mM-solution without shear shows a weak correlation peak at a momentum transfer of 0.09 nm^–1 which has its origin in the micellar interaction. For shear rates above a threshold value of =40 s^–1 the scattering pattern shows an irregular increase in anisotropy. The analysis of the anisotropic pattern reveals the existence of two types of micelles: Small rodlike micelles which are weakly aligned and very large rodlike aggregates which are strongly aligned and which are present above the threshold value of. The two micelles are in equilibrium with each other and the equilibrium shifts with increasing shear rate to the side of the large oriented micelles.     

Interactions of proteins with uniform colloidal hematite and chromium hydroxide particles. I. Adsorption

The adsorption of ovalbumin, -globulin, and lysozyme on uniform spherical hematite and chromium hydroxide particles in aqueous media has been studied as a function of the pH at a constant ionic strength. The uptake of ovalbumin and -globulin was greatest at their isoelectric points and differed little at 10^–2 and 10^–3 mol dm^–3 NaNO₃. The adsorption of lysozyme was strongly influenced by the ionic strength.The deposition of ovalbumin on hematite in the presence of Mg (NO₃)₂ was significantly greater than that with NaNO₃ under otherwise comparable conditions. Dialysis experiments with ovalbumin against magnesium nitrate solutions showed Mg²⁺ to be specifically bound to the protein.The shapes of isotherms indicated monolayer coverage for ovalbumin and multilayer coating for lysozyme for both adsorbents. The shapes of isotherms of -globulin on hematite point to a rearrangement of the protein on the particle surface, while a monolayer was found on chromium hydroxide particles.Supported by the NSF Grant CHE-9108420Part of a Ph.D. thesis     

Reversible aggregation Part I. Reversible flocculation monitored by turbidity measurements

The aggregation of four separate polystyrene latices, ranging in diameter from 210 nm to ca. 1 m, using sodium chloride and magnesium sulphate as the electrolytes, has been examined turbidimetrically. The reversibility of the aggregation was examined using a dialysis technique. It was found that for large particle size latices, diameters 781 nm and 1 m, aggregation was reversible in sodium chloride even at concentrations up to 0.5 mol dm^–3. The aggregation of smaller particles was not reversible. The aggregation of large particles in magnesium sulphate solutions was not readily reversed by dialysis. The latter result does not appear to agree with theoretical predictions.Dedicated to Professor Dr. Armin Weiss on the occasion of his 60th birthday.     

Interactions in multicomponent systems containing surfactants. System silver iodide — methylene blue and sodium dodecyl sulphate

The precipitation and dissolution of AgI in the presence of methylene blue (MB · Cl) and sodium dodecyl sulphate (NaDS) was followed by X-ray diffraction analysis.At high MB · Cl concentration, the absence of AgI precipitates was observed, which is explained by considering the redox process MB⁺ + 2I^– MB^– + I₂. The decrease in I^– concentration causes dissolution or inhibition of growth of solid AgI which is significant at relatively high MB · Cl concentrations. The addition of NaDS causes the disappearance of these effects, which is explained by the incorporation of MB in NaDS micelles.These explanations are supported by the potentiometric measurements using Ag/Ag₂S and Pt electrodes.