Static and dynamic light scattering from polystyrene/cyclohexane/toluene solutions

Summary Static and dynamic light scattering data from polystyrene in cyclohexane and toluene mixed solvent are reported. It is found from the Zimm plot analysis of the static data that if the subtraction of solvent signal is made properly then, the results are consistent with those in toluene indicating a preferential adsorption of the good solvent. Contin analysis of the dynamic data yields two modes unlike the dynamics of polystyrene in single solvent solutions which exhibit a single mode at all polymer concentrations covered here. A possible interpretation of the fast and slow modes is given. Keywords: Mixed Solvent; Dilute Polymer Solution; Preferential Adsorption; Static and Dynamic Light Scattering; Relaxation Modes. Received: 28 May 1999/Accepted: 8 September 1999     

Static and dynamic light scattering study of strong intermolecular interactions in aqueous solutions of PVP/C60 complexes

The investigations of the dilute aqueous solutions of polyvinylpyrrolidone/fullerene (PVP/C₆₀) complexes by static (SLS) and dynamic (DLS) light scattering showed that strong intermolecular interactions, effective on the distances of about 45-50 nm, take place in the solutions. Two concentration ranges are well distinguished in these solutions. Above a critical concentration (c_cr) the fluctuations in the solutions are hindered and only one, diffusive, mode is observed in DLS experiments. Upon dilution (c<c_cr) this unified structure divides into large fragments (domains) and the slow mode attributed to long-range concentration fluctuations, gradually appears. The angular and concentration dependencies of the diffusion coefficient of the slow mode indicate the existence of strong intermolecular interactions.     

Characterization of magnetic nanoparticle by dynamic light scattering

Here we provide a complete review on the use of dynamic light scattering (DLS) to study the size distribution and colloidal stability of magnetic nanoparticles (MNPs). The mathematical analysis involved in obtaining size information from the correlation function and the calculation of Z-average are introduced. Contributions from various variables, such as surface coating, size differences, and concentration of particles, are elaborated within the context of measurement data. Comparison with other sizing techniques, such as transmission electron microscopy and dark-field microscopy, revealed both the advantages and disadvantages of DLS in measuring the size of magnetic nanoparticles. The self-assembly process of MNP with anisotropic structure can also be monitored effectively by DLS.     

Dilute solution properties of pullulan by dynamic light scattering

Summary Pullulan, produced by the fungus Aureobasidium, has been studied in dilute solution by viscometry, static low angle light scattering and dynamic light scattering at temperatures of 25, 40, 60 and 80 °C. The samples used were fractions obtained by partial hydrolysis of native pullulan and successive fractionation with ethanol. The mass-average molar mass, M_W, of the studied pullulans were in the range of 1.67*10⁵ to 1.0*10⁶ g/mol. The translational diffusion coefficient at infinite dilution, Do, was obtained from the reduced first cumulant of the intensity autocorrelation function of the light scattered by extrapolation to zero scattering angle and zero polymer concentration. The activation energy of diffusion, E_D, of pullulan macromolecules was calculated from Do=D^oexp(-E_D/RT). It was found that in the given temperature rangeE_D = 16.5 ± 0.5 kJmol⁻¹ for all samples. Dedicated to Prof. Dragutin Fleš on the occasion of his 70th birthday     

Investigation of polyacrylonitrile solution inhomogeneity by dynamic light scattering

Dynamic light scattering (DLS) has been used to quantify nanoscale heterogeneity in the industrially significant polyacrylonitrile (PAN) polymer solution. The heterogeneity in polymer solution, traced by the ratio of amplitudes of the slow to fast mode, is observed to be related to various parameters, such as molecular weight of the polymer, the type of co‐monomer, processing time, concentration of the solution, and the choice of the solvents. It has been identified that low molecular weight PAN homopolymer have the least heterogeneity issues. Amongst the chosen co‐polymers for this study, similar degree of heterogeneity was observed at concentration slightly above the critical concentration at which the polymer chains begin to overlap. Whereas, at higher concentration, PAN‐methacrylic acid (4 wt%) copolymer showed the least heterogeneity issue. The aggregate diffusion coefficient of PAN‐methacrylic acid (4 wt%) copolymer solution in dimethylformamide (DMF) and N,N‐dimethylacetamide (DMAc) are respectively determined to be ～1.6 × 10^?12 cm²/s and ～1.6 × 10^?13 cm²/s, which results in an estimated aggregate size of 9 nm and 90 nm. POLYM. ENG. SCI., 55:1403–1407, 2015. © 2015 Society of Plastics Engineers     

Enhanced light scattering in coatings templated with interfacially stabilized colloids

Controlling inter-pore distances enables tuning the color or whiteness of microvoid coatings. While pore spacings have been modified in limited area inverse opal films, little work has occurred studying the feasibility of controlling pore spacings and thus the appearance of scalable, spray-on, microvoid inorganic coatings. In this work we investigated using interfacially stabilized colloidal templates to increase pore spacing and thus enhance Mie scattering in porous silica films. Coatings were fabricated by forming monodisperse colloids with or without a polyvinylpyrrolidone (PVP) interfacial stabilizing layer, dispersing them in a silica precursor solution, and spraying this suspension on a substrate. The films were cured and the colloids subsequently solution extracted at mild temperatures to create porous surfaces. Coatings made with PVP coated colloids had thicker pore walls and scattered light approximately 3× more efficiently than coatings made with bare colloids. Furthermore, a viewing angle dependent color shift was observed in the PVP colloid templated coatings. Side illumination of the samples with white light causes an orange appearance under angles of specular reflection, while a light blue appearance is observed out of these angles because of strong Mie scattering of short-wavelength radiation in both situations. Lastly, modeling based on Mie scattering confirms that it is the dominant optical effect in these coatings and explains the appearance of these coatings. The approach of using interfacially stabilized colloids to improve pore separation applies to many porous films and should be considered when increased light scattering is desired.     

Microgelation of unsaturated polyester resins by static and dynamic light scattering

The microgelation phenomenon during the curing of unsaturated polyester resin was investigated by both static and dynamic light scattering before gelation. The results of static light scattering revealed that the polymer molecular weight increased with degree of curing. The second virial coefficient, A₂, decreased slowly in the initial stage of curing and decreased dramatically at a conversion around α ∼ 8.7%, indicating a drastic decrease of compatibility between the polyesters and styrene. Two modes of the size distribution of the microgel particles during curing were observed by dynamic light scattering. The small particles consist of primary unsaturated polyester molecules. The large ones consist of microgel particles formed by linking adjacent polyester molecules. The sizes of the microgel particles increased in the initial stage of curing, then decreased slightly at a conversion of α ∼ 8.7%, which was due to the intramolecular crosslink reaction of the microgel particles. The experimental results revealed that the compatibility between polyesters and the styrene monomer became worse as the intramolecular crosslinking reaction inside the microgel particles caused a tight packing of the micro-gel molecules. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 871–878, 1998     

Static and dynamic light scattering studies of the crystallization of poly(ethylene oxide) from dilute solutions

We have monitored in situ the self-seeded crystallization of poly(ethylene oxide) from dilute toluene solutions by dynamic light scattering. In supercooled dilute solution, the radii (R) of the crystals grow linearly with time. the rate constant obtained from the slope of the plot R versus time depends on the temperature and the molecular weight of the polymer, both of which determine the degree of the supercooling. The maximum crystal size obtained from solutions of fixed concentration also depends on the temperature and the polymer molecular weight. It appears that crystal growth is limited because of molecular weight fractionation. Static light scattering from suspensions of stable crystals provides information on the crystal morphology. A comparison of experimental and theoretical particle scattering functions suggests that the crystals form short cylinders and that the crystal growth from the seeds is primarily two-dimensional. Some comparisons to melt crystallization are possible. The preparation and use of tiny seed crystals is critical to the success of these studies.     

Electrophoretic,dynamic, and static light scattering on charged polymer emulsions

Light scattering studies on dispersions formed by phase separation of a polymer-solvent-non-solvent mixture show that the dispersions comprise charged droplets of the polymer-rich phase. The charge number is not large, and data on the electrophoretic-scattering and the dynamic scattering in the absence of an external electric field are both consistent with distribution of charge among the droplets. Data on the dependence of the static scattering on concentration and scattering angle show that the droplets are also disperse in radius. The data are discussed in terms of an interaction potential among the charged droplets relating the electrostatic interactions to the charge number and radius of the droplets, and the ionic strength of the solvent.     

Dynamic light scattering of dilute PVA-borax aqueous solutions

Poly(vinyl alcohol)-borate (PVA-borate) complexes in dilute aqueous solutions were investigated by dynamic light scattering (DLS). Two relaxation modes obtained, were scattering vector-q² dependent and diffusive. The amplitude of slow mode was independent of borax concentration. In the very dilute PVA concentration regime ( [PVA] < 5 g/L), the PVA di-diol-borate complexation was dominated by intra-molecular reaction, and the fast mode correlation length ς_f which corresponds to the polymer chain dimension increased rapidly with borax concentrations lower than 0.06 M, and reached an asymptote in the higher borax concentration regime. However, for a dilute PVA aqueous solution with higher PVA content (i.e., [PVA] = 9 g/L), both intra-and inter-molecular PVA di-diol-borate complexations might happen. The chain expansion and shrinkage of PVA-borate complex with increasing borax concentration was observed due to the balance between the electrostatic repulsion of the charged diol-borate complexes and the intra-molecular crosslink induced by the intra-molecular di-diol-borate complexation.     

Particle diffusion in porous media investigated by dynamic light scattering

Dynamic light scattering as a non-invasive method was applied to the investigation of the diffusion of polystyrene (PS) particles in controlled pore glasses (CPG) as a function of the tracer particle to pore size ratio. These micro-/macro-porous glasses exhibit a bicontinuous randomly distributed microstructure and were saturated with mixtures of water and dimethylsulfoxide (DMSO) to achieve almost perfect optical matching. While the scattering of the glassy matrix vanishes under such conditions the polystyrene tracer particles show a suitable scattering intensity allowing for the implementation of a homodyne detection scheme. In the experiments two distinct diffusion modes can be identified which are related to the diffusion in the voids of the CPG grains and inside the CPG matrix, respectively, where the latter is significantly lowered in comparison to the free bulk diffusion. The diffusion coefficients within the confinement are quantified on basis of the ratio of particle to pore sizes.     

Cooperative and self-diffusion of polymers in semidilute solutions by dynamic light scattering

The quasielastic light scattering from semidilute solutions of polystyrene in tetrahydrofuran has been measured and we observe two distinct exponential decays separated by several orders of magnitude. The angular dependence of the decay constants is indicative of diffusive processes which we identify with the cooperative diffusion coefficient, D_c and the self diffusion coefficient D_s. It is found that D_c, identified with the fast decay, increases with polystyrene concentration and is independent of molecular weight. However, D_s decreases sharply with concentration and molecular weight. An explanation is given for the light scattering detection of these two diffusion coefficients which is based only on the assumptions inherent in the reptation model. In a limited region of molecular weight and concentration the experimental results appear to be consistent with the predictions of scaling theory.     

Dissolution and enzymatic hydrolysis of casein micelles studied by dynamic light scattering

The effects of temperature, ionic strength, and enzymatic hydrolysis on the average hydrodynamic radius (R _h) of casein micelles in phosphate buffer were studied by using dynamic light scattering. The results showed that the average R _h value of casein micelles decreased irreversibly during the heating, decreased with the increase of ionic strength in lower ionic strength solution (less than 0.05 mol/L), but opposite in higher ionic strength solution (above 0.1 mol/L). The R _h value of casein increased rapidly during the process of enzymatic hydrolysis, and the structural model of casein micelles in the enzymatic hydrolysis process was also proposed, i.e. the casein micelle changed from compact sphere into unfolded and regularly flocky peptides. Translated from The Chinese Journal of Process Engineering, 2006, 6(4), 615–618 [译自: 过程工程学报]     

Real-time dynamic light scattering on gelation and vitrification

The time-resolved dynamic light scattering has been employed to investigate gelation of divinylbenzene (DVB; branched chains) and vitrification of styrene (St; linear chains) during radical polymerization in bulk. The intensity correlation function (ICF) was obtained every 30 s during polymerization process. The DVB system exhibited a power law behavior in ICF characteristic of gelation threshold, which was followed by vitrification. In the case of St, two relaxation modes appeared before vitrification, which were assigned to be the cooperative and the slow relaxation modes.     

Viscoelastic characterization of moderately concentrated polystyrene solutions by dynamic light scattering

The dynamic light scattering measurements were performed for moderately concentrated entangled solutions of atactic polystyrene in benzene (BZ) at 25.0 °C, in cyclohexane (CH) at 34.5 °C (Θ), and in diethyl malonate (DEM) at 35.0 °C (Θ) to characterize their viscoelastic properties. The results have shown that while the mutual diffusion coefficient D increases in the BZ solutions and decreases in the CH and DEM solutions with increasing polymer mass concentration c, the friction coefficient ζ for the three solutions increases with c showing the same power-law behavior irrespective of the weight-average molecular weight M_w and solvent quality. It has been found that the instantaneous longitudinal modulus L₀ for the CH and DEM solutions increases in proportion to c², obeying the familiar relation for the plateau value (4/3)G_N of the longitudinal stress relaxation modulus, but the L₀ values for these solutions are somewhat smaller than the values predicted from the relation. The terminal relaxation time τ_m for the two Θ solvent systems has been found to follow the power-law τ_m∝c^2.7, showing good correspondence to the relation established by rheological measurements.     

Characterization of spatial inhomogeneities and dynamic properties of random cross-linked polystyrene networks by dynamic light scattering

The network inhomogeneity and the cooperative motion of the network chains of random cross-linked poly(styrene-co-maleic anhydride) gels were investigated by dynamic light scattering. Measurements were performed for gels in the preparation state as well as in the swelling equilibrium. Network inhomogeneities and cooperative motion were analyzed at varying the cross-linker concentration and the polymer volume fraction. While the cross-linker concentration has only a minor influence on the inhomogeneity and the diffusion constant D_coop, the polymer volume fraction clearly influences both measured properties. The concentration dependence of D_coop can be well described by a power law, as known for semi-dilute polymer solutions. In the preparation state the networks appear homogeneous, exhibiting dynamic contributions to the scattering intensity of 70-90%. Swollen to equilibrium stage, significant heterogeneities emerge, reducing the dynamic contributions to 10-20%.     

Interaction of nanogel with cyclodextrin or protein: Study by dynamic light scattering and small-angle neutron scattering

The structure of hydrogel nanoparticles (CHP nanogels), formed by self-aggregation of cholesterol-bearing pullulan (CHP) was studied by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The interactions between the CHP nanogel and methyl-β-cyclodextrin (CD) or protein (hen egg white) were also investigated. It was revealed by SANS that the nanogels were spherical in shape with a radius of 6.7 nm. The following two functions were disclosed. (1) CHP nanogels were dissociated by the addition of CD and formed inclusion complexes with cholesteryl groups, leading to suppression of hydrophobic interaction between the cholesteryl groups. (2) The nanogel behaved as a molecular chaperone (heat shock protein-like activity) when CHP nanogel was mixed with hen egg white and heated up to 75 °C. The egg white aqueous solutions with CHP nanogel remained transparent while the egg white without CHP nanogel became opaque.     

聚氨基甲酸酯-聚脲微胶囊的动态光散射研究

利用界面聚合法制备了聚氨基甲酸酯-聚脲微胶囊,分析了水相乳化剂含量、反应单体摩尔比及二醇类分子量对微胶囊粒径分布的影响。结果表明,平均粒径随PVA含量增加而减小,且粒径分布较为狭窄;PVA含量为2%时,平均粒径为13.35μm。平均粒径随单体摩尔比增加而增大,摩尔比为6∶5∶1时,粒径分布对称性良好且较为狭窄,平均粒径为13.35μm。平均粒径随软链节增加而增大,且粒径分布较为宽广;以EG、HD、PEG 300、PEG1000和PEG 2000为软链节时,平均粒径分別为8.25,11.66,13.35,15.09,16.36μm。     

Fast internal dynamics in polyelectrolyte gels measured by dynamic light scattering

Summary Dynamic light scattering was used to investigate the dynamics of sodium poly(styrene sulfonate) and fully neutralized poly(acrylic acid) gels as a function of the degree of swelling and weight ratio of cross-linking agent. It was shown that the collective diffusion coefficient increases with increasing degree of swelling and that the diffusion coefficient shows stronger concentration dependence than predicted by scaling arguments. For gel samples measured at the swelling equilibrium, the diffusion coefficient increases with increasing gel concentration for both gel systems.