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Showing papers in "Colloid and Polymer Science in 1994"


Journal ArticleDOI
TL;DR: The typical phase behavior of microemulsion systems undergoing phase inversion is briefly reviewed in this article, where the mean and Gaussian curvatures of the interfacial film with temperature are determined.
Abstract: The typical phase behavior of microemulsion systems undergoing phase inversion is briefly reviewed. As a model system H2O-n-octane-C12E5 is studied with various experimental techniques. The occurring microstructures are visualized by freeze fracture electron microscopy and the corresponding domain sizes are quantified by small-angle neutron scattering. From the variations of the domain sizes the mean and Gaussian curvatures of the interfacial film with temperature are determined. It is found that the mean interfacial curvatureH changes gradually and nearly linearly with temperature from positive (Winsor I) to negative (Winsor II), passing through zero for bicontinuous microemulsions where these contain exactly equal volume fractions of water and oil. There the interfacial tension between bulk water-and oil-rich phases passes through an extreme minimum. Quantitative knowledge of the curvatures permits the measurements of interfacial tensions between the bulk phases to be discussed in terms of the relative contributions of bending energy and entropy of dispersion.

486 citations


Journal ArticleDOI
TL;DR: In this paper, the conversion versus time curves were measured for poly(N-isopropylacrylamide) microgel latexes prepared by polymerization in water with sodium dodecyl sulfate, SDS.
Abstract: Conversion versus time curves were measured for poly(N-isopropylacrylamide) microgel latexes prepared by polymerization in water with sodium dodecyl sulfate, SDS. Polymerization rates increased with temperature with methylenebisacrylamide crosslinking monomer consumed faster thanN-isopropylacrylamide. The particle diameter decreased with increasing concentrations of SDS in the polymerization recipe and there was evidence that the rate of polymerization increased somewhat with SDS concentration. Particle formation occurred by homogeneous nucleation as micelles were absent.

388 citations


Journal ArticleDOI
TL;DR: In this article, the principle of maximum pressure in a bubble for measurements of dynamic surface tension is realized in a fully automatically operating apparatus, which can be temperature controlled from 5° to 80°C.
Abstract: The principle of maximum pressure in a bubble for measurements of dynamic surface tension is realized in a fully automatically operating apparatus. The set-up yields data in the time interval from 1 ms up to several seconds and can be temperature controlled from 5° to 80°C. Experimental data obtained for different surfactants and gelatine in water and/or water/glycerine mixtures at different temperatures are discussed. A direct comparison with results from oscillating jet and inclined plate experiments shows excellent agreement.

151 citations


Journal ArticleDOI
T. Hayashita1, T. Kurosawa2, T. Miyata2, K. Tanaka2, Manabu Igawa2 
TL;DR: In this paper, cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively.
Abstract: The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R2=C2H4, R3=C4H9) and 9 (R2=C4H8, R3=C2H5) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation.

148 citations


Journal ArticleDOI
TL;DR: In this article, the brittle fracture behavior of amorphous poly(lactide) copolymers has been investigated and the draw ratios of poly(L-lactides) and non-crystallizable L/D lactide networks were investigated.
Abstract: The observed brittle fracture behavior of amorphous polylactides seems to be contradicted by the low value ofC ∞ =2 determined for poly(L-lactide) by Flory and coworkers. Such very flexible polymer chains deform by shear yielding, and fracture in a ductile manner. In this study,C ∞ was estimated in a number of ways, resulting in much higher values ofC ∞ =11.7 andC ∞=9.1 for poly(L-lactide) and L- and D-lactide copolymers, respectively. These high values ofC ∞ and the low entanglement density account for the brittle fracture behavior of amorphous poly(lactide), as well as for the maximum attainable draw ratios of poly(L-lactide) networks and melt spun fibers. Bulk polymerized poly(L-lactide) networks, where crystallization during polymerization impedes severe entangling, could be hot-drawn most effectively to draw ratios of 8–16, resulting in very strong materials with tensile strengths of 550–805 MPa. By comparison, amorphous, non-crystallizable L/D lactide networks, which do not crystallize during polymerization, could be drawn less, to λ=7. These materials with strengths up to 460 MPa could, nevertheless, be oriented much more effectively than linear, amorphous L/D lactide copolymers.

130 citations


Journal ArticleDOI
TL;DR: In this paper, a new synthetic process to prepare composite particles with multilayers, comprised of usual polymer latices, ultra-fine magnetic particles, and a polystyrene layer was examined under various solution conditions.
Abstract: A new synthetic process to prepare composite particles with multilayers, comprised of usual polymer latices, ultra-fine magnetic particles, and a polystyrene layer was examined under various solution conditions.

90 citations


Journal ArticleDOI
TL;DR: In this article, the surface and bulk structures of polyvinyl alcohol (PVA) hydrogels were investigated by scanning electron microscopy using Froeze-etching and critical point drying (CPD) techniques.
Abstract: Froeze-etching (FE) and critical point drying (CPD) techniques were employed to prepare samples for investigating surface and bulk structures of polyvinyl alcohol (PVA) hydrogels by scanning electron microscopy. The hydrogels were obtained by freezing homogeneous solutions containing PVA polymer in either water or an aqueous solution of dimethyl sulfoxide (DMSO). An oriented porous structure was observed in the PVA hydrogel prepared without DMSO. The structure on the surface was found to be more porous than in the bulk for PVA hydrogels prepared from aqueous DMSO solutions. For given compositions of the hydrogels, samples prepared by FE technique showed a highly porous fibrillar structure on the surface, while those prepared by CPD technique showed a collapsed fibrillar structure with much less porosity. This marked difference indicates a collapse of the surface structure caused by the CPD technique. The CPD technique also led to significant reduction in porosity and loss of fibrillar structure in the bulk. Volume shrinkage of hydrogels caused by dehydration in ethanol may be responsible for the surface collapse as well as alteration of bulk structure. The FE technique reveals a more native structure of hydrogels than the commonly used CPD technique. However, it suffers from disadvantages such as charging and structural damage at high magnifications.

82 citations


Journal ArticleDOI
TL;DR: A theoretical analysis of transient isothermal crystallization, including relaxational and athermal effects is given in this paper, based on Kolmogoroff-Avrami-Evans transformation equation and nucleation theory of Turnbull and Fisher.
Abstract: A theoretical analysis of transient isothermal crystallization, including relaxational and athermal effects is given The analysis is based on Kolmogoroff-Avrami-Evans transformation equation and nucleation theory of Turnbull and Fisher The memory of previous structures manifests itself in the distribution of atomic (molecular) clusters which determines the initial number of crystal nuclei and the initial rate of thermal nucleation

81 citations


Journal ArticleDOI
TL;DR: In this article, two sets of comb-grafted polymeric surfactants based on poly-(methylhydrogen siloxane) (PHMS) and/or poly(dimethylsiloxane), were prepared by sililation of the active Si-H group with an active omega-vinyl group of specially designed undecenoic-polyethyleneglycol esters.
Abstract: Two sets of comb-grafted polymeric surfactants based on poly-(methylhydrogen siloxane) (PHMS) and/or poly(dimethylsiloxane) (PHMS-PDMS) were prepared by sililation of the active Si-H group with an active omega-vinyl group of specially designed undecenoic-polyethyleneglycol esters (UPEG) to form “newly-designed” polysiloxane-grafted-polyethyleneglycol comb-copolymeric surfactants.

70 citations


Journal ArticleDOI
TL;DR: In this paper, the authors make creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, and they find that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance.
Abstract: By making creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, we have found on decreasing temperature towardsT g that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance. This behavior is exactly the same as previously observed in low molecular weight poly(styrene), proving that this spectacular anomaly in the viscoelasticity of low molecular weight polymers is general and deserves an explanation. Photon correlation spectroscopic measurements performed on the same sample have extended the observation of the viscoelastic response to shorter times and the result corroborates the trend of variation established by the creep data.

69 citations


Journal ArticleDOI
TL;DR: Amino-functionalized latex particles were obtained batchwise by emulsion copolymerization of styrene and vinylbenzylamine hydrochloride (VBAH) in the presence of 2-2′-Azobis(2-amidinopropane) HCl (V50) as discussed by the authors.
Abstract: Amino-functionalized latex particles were obtained batchwise by emulsion copolymerization of styrene and vinylbenzylamine hydrochloride (VBAH) in the presence of 2-2′-Azobis(2-amidinopropane) HCl (V50). Size monodispersity of the particles was improved by using divinylbenzene (DVB) as a third monomer at a 2% molar ratio. Surface amino group titration was performed spectrometrically with N-succinimidyl 3-(2 pyridyldithio)propionate (SPDP). The yields of functional monomer incorporation were up to 85%.

Journal ArticleDOI
TL;DR: In this paper, an experimental and theoretical investigation of the overall crystallization kinetics of thin polymer films containing transcrystalline regions on their surfaces is presented, where typical features of crystallization curves can be associated with the occurrence of trans-crystallinity.
Abstract: An experimental and theoretical investigation of the overall crystallization kinetics of thin polymer films containing transcrystalline regions on their surfaces is presented. DSC experiments on polyamide 6-6 show that typical features of crystallization curves can be associated with the occurrence of transcrystallinity. In order to interpret these experimental results, a theoretical model is built within the frame of overall crystallization kinetics theories. It makes it possible to correlate the thickness of transcrystalline zone both to the crystallization temperature, the shape of the peak and the density of nuclei within the polymer. Computer simulation is also used to describe the different steps of structure development within a thin film containing transcrystalline regions.

Journal ArticleDOI
TL;DR: At high alcohol contents montmorillonite-alcohol complexes (interlayer solvates) are formed and the colloidal dispersions become unstable even in the absence of salt.
Abstract: The critical coagulation concentration,cK, of sodium chloride for sodium montmorillonite dispersed in water (solid content 0.025 percent) is 8 mmol/L. It remains virtually constant (7.5–8.5 mmol/L) in water-rich alcohol mixtures (below 50% (v/v) methanol and 40% ethanol and propanol). At higher alcohol contents thecK decreases to 3.6 mmol/L (70 percent methanol), 1.2 mmol/L (70 percent ethanol), and 0.8 mmol/L (60 percent propanol). In the presence of 10−4 M sodium diphosphate thecK in water rises to 195 mmol/L. In contrast to the behavior in the absence of diphosphate, even small amounts of alcohol reduce the critical coagulation concentration. In 70% methanol thecK is 7.5 mmol/L, in 70 percent ethanol 2.5 mmol/L and in 60% propanol 5 mmol/L. The main mechanism is coagulation by contacts between negatively charged edges and faces.

Journal ArticleDOI
TL;DR: In this paper, a mixture of poly(ethylene terephthalate) and poly(methylene-2,6-naphthalene dicarboxylate) was obtained by coprecipitation from solution followed by melt-pressing for different timestaplemand quenching in iced water.
Abstract: Blends of poly(ethylene terephthalate) (PET) and poly(ethylene-2,6-naphthalene dicarboxylate) (PEN) were obtained by coprecipitation from solution followed by melt-pressing for different timest mand quenching in iced water. When the melt-pressing time was 0.2 and 0.5 min, two glass transition temperaturesT gwere observed by means of dynamic mechanical analysis (DMA), indicating that there are two phases present, a PEN-rich phase and a PET-rich phase. The differential scanning calorimetry (DSC) curves show two crystallization peaks and two melting peaks which, according to wide-angle x-ray scattering (WAXS) measurements, can be attributed to PET and PEN, respectively. In the case oft m=2 min or longer, a single value ofT gand thus a single phase is found to exist. Fort m=10 min and 45 min no crystallization and melting at all is observed during heating with 10°C/min, indicating that a copolyester of PET and PEN has been formed by transesterfication during melt-pressing. Time-resolved WAXS measurements during isothermal crystallization show that, in the blend, the half-time of crystallization of PET is different from that of PEN, and not the same as that which is found in the pure polymer.

Journal ArticleDOI
TL;DR: In this paper, micron-size polystyrene/poly(styrene-divinylbenzene) composite particles were produced by seeded copolymerization of S and DVB with 2,2′-azobisisobutyronitrile as an initiator in the ethanol/water medium in the presence of 2.37 μm-size monodisperse PS seed particles produced by dispersion polymerization.
Abstract: Micron-size monodisperse polymer particles having multihollow structures were prepared as follows. First, micron-size monodisperse polystyrene/poly(styrene-divinylbenzene) (PS/P(S-DVB)) composite particles were produced by seeded copolymerization of S and DVB with 2,2′-azobisisobutyronitrile as an initiator in the ethanol/water (76/24, weight ratio) medium in the presence of 2.37 μm-size monodisperse PS seed particles produced by dispersion polymerization. The molar ratio of S/DVB was changed in the range of 1/1∼10/1. The uncrosslinked polymer within the composite particles was extracted with toluene under reflux. For the highest DVB content (S/DVB=1/1, molar ratio), one large hollow was observed in a part of the composite particles after the extraction. For the middle DVB content (S/DVB=4/1, molar ratio), multihollow structure was observed in all the particles. For the lowest DVB content (S/DVB=10/1, molar ratio), fine multihollow structure was observed in all the particles.

Journal ArticleDOI
TL;DR: In this paper, a series of cyclic and linear polydimethylsiloxanes (PDMS) of various molecular weights ranging from 300 to 10 000 g/mol in the temperature range above the glass transition (from 130 K to 190 K) was studied.
Abstract: Dielectric spectroscopy (10−1 Hz to 107 Hz) has been employed to study the molecular dynamics of a series of cyclic and linear polydimethylsiloxanes (PDMS) of various molecular weights ranging from 300 to 10 000 g/mol in the temperature range above the glass transition (from 130 K to 190 K). The observed α-relaxation depends strongly on both molecular weight and structure of the samples. For linear PDMS oligomers, the α-relaxation shifts towards lower temperatures with decreasing molecular weight in good accordance with the Fox-Flory-model. Cyclic PDMS reveals a qualitatively different molecular weight dependence: for a given temperature the α-relaxation time increases with decreasing ring length, but has a maximum for small oligomers (degree of polymerizationn≈6). The shape of relaxation curves and, with it, the relaxation time distribution is independent from length and architecture of the chains The observed experimental findings are in qualitative agreement with dynamic Monte-Carlo simulations.

Journal ArticleDOI
TL;DR: In this article, point curves and θ temperatures for poly(vinylpyrrolidone) at several concentrations for a variety of inorganic salts (phosphates, monohydrogen phosphates, sulfates, carbonates, dihydrogen phosphate and fluorides) were determined.
Abstract: Cloud point curves and θ temperatures have been determined for aqueous solutions of poly(vinylpyrrolidone) at several concentrations for a variety of inorganic salts (phosphates, monohydrogen phosphates, sulfates, carbonates, dihydrogen phosphates and fluorides). The resulting dependency of the critical temperatures θ (mostly between 289 and 350 K) on the molar concentration can be expressed as sequences showing the decreasing effect of anion species or cation species in salting out the polymer. The decreasing order of effectiveness of the anions in reducing the θ temperatures is PO 4 3− >HPO 4 2− >SO 4 2− ≈CO 3 2− >H2PO 4 − >F−. The order for cation is Na+>K+. The changes brought about in θ temperatures by the salts were found to be the results of the changes taking place in the hydrophilic and hydrophobic interactions among polymer, solvent and additive salts and of the change of water structure by structure making or structure breaking ions, and of the influence of salts on the hydration sheath of the polymer.

Journal ArticleDOI
TL;DR: In this paper, a cation adsorption model is presented and its recent applications are discussed, which combines electrostatic equations with specific binding, and considers neutral and positively charged complexes between the negative surface sites and organic cations in a closed system.
Abstract: A cation adsorption model is presented and its recent applications are discussed. The model combines electrostatic equations with specific binding, and considers neutral and positively charged complexes between the negative surface sites and organic cations in a closed system. Extensions in the model account for dye aggregation in solution, and for the formation of solution complexes of inorganic cations, such as [M++ Cl−]+. The amounts of 45Ca2+ adsorbed to vesicles extracted from the plasma membranes of melon root cells could be adequately simulated and predicted. The binding coefficients determined for Ca2+, Na+, and Mg2+ are in the range of values previously deduced for binding to phospholipid components. Model calculations were applied to the test of hypotheses on the effect of salt stress on the growth of roots. The adsorption of monovalent organic cations to montmorillonite is characterized by binding coefficients that are at least six orders of magnitude larger than those of Na+, Mg2+, Ca2+, and Cd2+, or those of CdCl+ or CaCl+. Monovalent organic cations were found to adsorb 140–200% of the cation exchange capacity of the clay and to cause charge reversal. Deductions from adsorption results of acriflavin are consistent with those drawn from the application of other experimental methods. Preliminary results on the adsorption of divalent organic cations are presented. Agro-environmental applications of organo-clays are discussed.

Journal ArticleDOI
TL;DR: The effect ofn-butanol,n-propanol, andn-hexanol on the critical micelle concentration and degree of ionisation of the micelles of dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromides in aqueous solution has been determined by conductimetric techniques.
Abstract: The effect ofn-butanol,n-propanol, andn-hexanol on the critical micelle concentration (CMC) and degree of ionisation of the micelles of dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromides in aqueous solution has been determined by conductimetric techniques. Increase of the molality of added alcohol over the concentration ranges examined (up to 0.3 mol kg−1 butanol, 0.07 mol kg−1 pentanol and 0.025 mol kg−1 hexanol) caused a progressive decrease of CMC and increase of the degree of ionisation for each surfactant-alcohol system. At a constant molality of added alcohol the degree of ionisation increased with a) an increase of the chain length of the surfactant for each alcohol and b) an increase of the chain length of the alcohol for each surfactant. The distribution of each alcohol between the aqueous and micellar phases and the free energy of solubilization were determined from the change of CMC with molality of added alcohol.

Journal ArticleDOI
TL;DR: In this paper, the surface structure of latex dispersion films was examined with an atomic force microscope and the results showed that after four months, the structure of the film did not change anymore.
Abstract: The surface structure of latex dispersion films was examined with an atomic force microscope. All measurements were done in air on latex films having a minimum film formation temperature of 12°C and a glass transition temperature of 18°C. One aim of this study was to follow structural changes during film formation. Three minutes after spreading the film, its surface layer dried. Afterwards, the structure of the film did not change anymore. Only after 4 months could structural changes be observed: Though individual latex particles could be identified, the particles partly melted into one another.

Journal ArticleDOI
TL;DR: In this paper, latex beads were determined with Ellman's reagent and the immunological activity of the sensitized latex was assessed with 14.14C iodoacetamide and anti C-reactive protein antibody.
Abstract: Emulsion copolymerization of styrene and a cationic monomer vinylbenzyl-isothiouronium chloride (VBIC) with initiation by 2,2′ azobis(2-amidinopropane)-dihydrochloride (V-50) gave monodisperse latex particles. After post-stabilization with cationic or non-ionic surfactants, the colloids were diluted in basic buffers with concomitant deprotection of the sulfhydryl groups. Therefore, coupling reactions on the latex beads were possible. Coupling conditions were determined with Ellman's reagent.14C iodoacetamide and anti C-reactive protein antibody Fab fragments were immobilized and finally, the immunological activity of the sensitized latex was assessed.

Journal ArticleDOI
TL;DR: In this article, a comparative study of the influence of anionic (sodium dodecyl sulfate, SDS), cationic (tetradecyltrimethylammonium bromide, TTAB) and non-ionic (penta-ethyleneglycol mono n-dodecyl ether, C12E5) surfactants on the structure and composition of adsorbed layers of Quatrisoft LM 200 on hydrophilic surfaces (mica and silica) was carried out using surface force apparatus andin situ null
Abstract: A comparative study of the influence of anionic (sodium dodecyl sulfate, SDS), cationic (tetradecyltrimethylammonium bromide, TTAB) and non-ionic (penta-ethyleneglycol mono n-dodecyl ether, C12E5) surfactants on the structure and composition of adsorbed layers of cationic hydrophobically modified hydroxyethylcellulose (Quatrisoft LM 200) on hydrophilic surfaces (mica and silica) was carried out using surface force apparatus andin situ null ellipsometry. It is shown that a complex interplay of electrostatic, hydrophobic, and steric effect govern polymer/surfactant/surface interactions and that the effect of surfactant addition strongly depends on its nature and concentration. Both anionic and non-ionic surfactants exhibit aggregation on the polymer hydrophobes. SDS has the most profound influence on Quatrisoft interfacial behavior due to the changes in electrostatics accompanying formation of the polymer/surfactant complex. In the case of C12E5, large surfactant clusters bound to the polymer affect the macromolecules' conformation in the adsorbed layer via steric effects. In contrast to SDS and C12E5, no evidence of interaction between the polycation and a like-charged surfactant, TTAB, was obtained. At the same time, TTAB adsorbs on the surface in competition with the polyelectrolyte. This results in partial displacement of the latter and its looser attachment to the surface.

Journal ArticleDOI
TL;DR: In this paper, the selfassembly of polyelectrolytes-polystyrenesulfonate (PSS) and polyallylamine (PAH) with added salts of MnCl and NaBr was studied by x-ray reflectometry and ellipsometry technique.
Abstract: Self-assembly of polyelectrolytes-polystyrenesulfonate (PSS) and polyallylamine (PAH) with added salts of MnCl and NaBr was studied by x-ray reflectometry and ellipsometry technique. The thickness of PSS-PAH bilayer was measured to be 5.1±0.2 nm according to reflectometry and 6.1±0.7 nm according to ellipsometry. The discrepancy in data is attributed to the difference in the interaction of the interfaces with x-rays and visible light. The films are found to be rather homogeneous and the deposition process regular. The refraction indices of the deposited films were found to ben0=1.50±0.05,k0=0.07±0.05,ne=1.53±0.05ke=0, optical axis being perpendicular to the surface. The values of refractivity characterize the whole film (up to seven bilayers) and do not vary with increasing thickness.

Journal ArticleDOI
TL;DR: In this paper, the structure and the sorption properties of partially hydrophobized silicates (dodecylammonium and dodecyldiammonium vermiculites) have been investigated in aqueous solutions of 1-butanol.
Abstract: The structure and the sorption properties of partially hydrophobized silicates (dodecylammonium and dodecyldiammonium vermiculites) have been investigated in aqueous solutions of 1-butanol. The alcohol is preferentially adsorbed on the surface. The interlayer composition is calculated from adsorption and x-ray diffraction data. In air-dried state the organic cations lie flat on the interlamellar surface. In aqueous butanol solutions, the basal spacing of dodecylammonium vermiculite gradually increases with the extent of butanol adsorption because the chains increasingly point away from the surface. The basal spacing of dodecyldiammonium vermiculite is virtually independent on the interlayer composition because the expansion of the interlayer space is sterically restricted and a relatively rigid structure is formed. The enthalpy of the displacement of water by 1-butanol has been determined by flow sorption microcalorimetry. The displacement process is endothermic.

Journal ArticleDOI
TL;DR: In this article, a turbidimetric analysis of particle interaction in latex suspensions is given, where the turbidity measured at different wavelengths λ can be rendered by the product of an integrated form factorQ(λ 2) and a suitably defined integrated structure factorZ(λ2,c).
Abstract: A turbidimetric analysis of particle interaction in latex suspensions is given. The turbidity measured at different wavelengths λ can be rendered by the product of an integrated form factorQ(λ2) and a suitably defined integrated structure factorZ(λ2,c). This factorization rests on the expansion of the form factor of the particlesP(q) and the structure factorS(q) [q=(4π/λ)sin(θ/2); θ: scattering angle] of the system in even powers ofq. The accuracy of this approximation has been shown by calculating the turbidity for a system of hard spheres in terms of the Percus-Yevick structure factor by numerical integration. Also, the effect of polydispersity has been taken into account within the frame of Percus-Yevick-Vrij theory for non-uniform hard spheres. It is shown that the influence of small polydispersity (standard deviation below 8%) is within experimental uncertainty. The method is applied to precise UV-spectra (400≤λ≤800 nm) obtained from a polystyrene latex with a diameter of 77.4 nm. The integrated structure factorZ(λ2,c) obtained experimentally can be interpreted in terms of an effective diameter of interaction giving a measure for the strength of electrostatic interaction.

Journal ArticleDOI
Alain M. Jonas1, Tp. Russell1, Dy. Yoon1
TL;DR: In this article, structural changes occurring during crystallization of quenched amorphous poly(ethylene terephthalate) (PET) and subsequent cooling/heating cycles have been studied by real-time small-angle x-ray scattering (SAXS), using synchrotron radiation.
Abstract: Structural changes occurring during crystallization of quenched amorphous poly(ethylene terephthalate) (PET) and subsequent cooling/heating cycles have been studied by real-time small-angle x-ray scattering (SAXS), using synchrotron radiation. Initial crystallization is found to occur by insertion of new lamellae between the existing ones, while rapid continuous melting/recrystallization happens when the cold-crystallized PET samples are heated above the previous highest annealing temperature. Such melting/recrystallization results in irreversible increases in the lamellar long period, the crystal thickness and the density difference between the crystalline and amorphous regions; in contrast, at temperatures below the prior highest crystallization temperature, the structural changes are dominated by reversible effects such as thermal expansion. However, throughout the entire temperature range up to the melting point around 250 degrees C, the crystal core thickness remains quite small, less than ca. 50 Angstrom, and the linear crystallinity of lamellar stacks remains nearly constant around 0.3. Such a low crystallinity indicates the presence of thick order-disorder interfacial layers on the lamellar surface, whose thickness increases with temperature.

Journal ArticleDOI
TL;DR: In this paper, the stability of thermoreversible microgel particles of poly(N-isopropylacrylamide) having carboxylate surface charge groups was studied in the presence of electrolyte and non-adsorbing polymer.
Abstract: The stability of thermoreversible microgel particles of poly(N-isopropylacrylamide) having carboxylate surface charge groups has been studied in the presence of electrolyte and non-adsorbing polymer. Methylation of the surface charge groups leads to a decrease in the electrophoretic mobility of the particles and also the interparticle electrostatic repulsive potential, resulting in the material becoming more susceptible to flocculation. The Hamaker constant of the microgel particles increases with the decrease in the hydrodynamic size of the particles following heating. This brings about an increase in the van der Waals attractive energy which results in the particles aggregating in the presence of sufficient electrolyte. Under conditions of flow through membranes, where shearing forces are operative, the flocculation observed following the heating of the dispersions results in the blockage of pores.

Journal ArticleDOI
TL;DR: In this article, the apparent molar volumes and adiabatic compressibilities of aqueous solutions of the amphiphilic tricyclic drugs, chlorpromazine, promethazine and imipramine have been determined from measurements of density and ultrasound velocity.
Abstract: The apparent molar volumes and adiabatic compressibilities of aqueous solutions of the amphiphilic tricyclic drugs, chlorpromazine, promethazine, promazine and imipramine have been determined from measurements of density and ultrasound velocity. Positive deviations of the apparent molar volume from the Debye-Huckel limiting law in dilute solution indicate possible premicellar association. The changes of molar volume and compressibility accompanying aggregate formation were appreciably smaller than those of typical surfactants, suggesting a more tightly packed aggregate. The magnitude of the increase in molar compressibility on micellisation of imipramine decreased with temperature rise between 20 and 35°C. The results are discussed in terms of the structure and hydration of the drug aggregates.

Journal ArticleDOI
TL;DR: In this article, phase diagrams of aqueous solutions of poly(N-vinyl caprolactam) copolymer with vinylamine (3.8 mol%) were shown to be binodal curves with lower critical solution temperatures (LCST) in the range 304-313.
Abstract: Phase diagrams of aqueous solutions of poly(N-vinyl caprolactam) (PVCL), N-vinyl caprolactam copolymer with vinylamine (3.8 mol%) (CP(VCL-VA)), and poly(N-vinyl propylacetamide) (PVPA) were shown to be binodal curves with lower critical solution temperatures (LCST) in the range 304–313.5 K and critical concentrations in the range of 0.02–0.08 polymer weight fraction. Aqueous solutions of N-vinyl caprolactam copolymer with N-vinyl pyrrolidone (80 mol%) (CP(VCL-VP)) remained homogeneous in the entire region of the liquid state of water. The enthalpy of mixing with water of PVPA and CP(VCL-VP) was negative and the curve was concave over the entire range of composition at 298 and 308 K. The excessive heat capacity and partial heat capacity at infinite dilution of PVPA were positive, proving the hydrophobic character of hydration of this polymer. In contrast, these parameters were negative for CP(VCL-VP), revealing hydrophilic hydration. Hydrophilic hydration was predominant in solutions which were homogeneous over a wide temperature range, whereas hydrophobic hydration predominated in solution of polymers with LCST.

Journal ArticleDOI
TL;DR: The observed mobility difference between the intact and apoptotic HL-60RG cells was found to be due mainly to the difference in friction exerted by the cell surface layers on the liquid flow around the cells between these two types of cells.
Abstract: We measured the electrophoretic mobilities of HL-60RG cells and their apoptotic cells triggered by Actinomycin D as a function of the ionic strength of the suspending medium at pH 7.4. Both types of cells showed negative mobilities. The apoptotic HL-60RG cells exhibited larger mobility values in magnitude than intact HL-60RG cells in the whole range of the electrolyte concentration measured. The obtained data were analyzed via a mobility expression for “soft particles’, that is, colloidal particles with ionpenetrable surface layers. The observed mobility difference between the intact and apoptotic HL-60RG cells was found to be due mainly to the difference in friction exerted by the cell surface layers on the liquid flow around the cells between these two types of cells rather than the difference in charge density in their surface layers. A possible explanation for this mobility change by apoptosis is given.