Fractal Characterization of Silica Sol Prepared by the Sol-Gel Method: From the Sol Formation to the Flocculation Process

The fractal characterization of silica particles prepared by the sol-gel method was obtained; from the beginning of the sol-gel synthesis to the aggregation process of these particles by adding metal ions in solution, the fractal dimension was determined. At the beginning of the sol-gel process, unstable structures were formed due, essentially, to the auto-catalytic nature of the sol-gel condensation reactions; these particles are fractal structures with a fractal exponent corresponding to a reaction limited aggregation regime. As the time proceeds, the reactants are consumed approaching the system to equilibrium, stabilizing the size of the silica particles. The silica sol can be flocculated by adding metal ions in solution. The fractal exponent for the aggregation process was determined, obtaining a value corresponding to a diffusion limited aggregation regime.     

壳聚糖不饱和羧酸盐聚集行为的研究

以半干法制备了一系列壳聚糖不饱和羧酸盐--壳聚糖水杨酸盐(a1)、壳聚糖苯甲酸盐(a2)、壳聚糖肉桂酸盐(a3)壳聚糖丙烯酸盐(a4)和壳聚糖衣康酸盐(a5).用红外光谱和紫外光谱表征了该产品的结构,以凯氏定氮法测定了羧酸的结合量.结果表明壳聚糖和不饱和羧酸盐是通过壳聚糖上的氨基和羧酸中的羧基发生了成盐反应,羧酸的结合...     

Investigations on the semi-batch precipitation of silica

The semi-batch precipitation process of silica from sodium silicate and sulphuric acid has been structured into a primary particle production stage, an aggregation process until the gel point is reached and finally a gel fragmentation and compaction process. The progress of aggregation was analyzed by photon correlation spectroscopy. The reaction limited aggregation kernel was found to be proportional to B'(t)(q(p - q))A/2, where A assumes the value of one. The quantity B'(t) varies between 3.4 x 10(-20) and 2.6 x 10(-20) 1/min and is only a weak function of time. The stability ratio W for the aggregation process decreases with increasing aggregate size. During the period after the gel point the gel fragmentates. The gel clusters have an initial fractal dimension of approximately 1.8 which rapidly increases to 2.4 and stays roughly constant until the end of the process. The specific surface area decreases from 480 to 300 m2/g. The primary particles have a uniform size of 22.7 nm.     

Detailed model of the aggregation event between two fractal clusters

A model has been developed for describing the aggregation process of two fractal clusters under quiescent conditions. The model uses the approach originally proposed by Smoluchowski for the diffusion-limited aggregation of two spherical particles but accounts for the possibility of interpenetration between the fractal clusters. It is assumed that when a cluster diffuses toward a reference cluster their center-to-center distance can be smaller than the sum of their radii, and their aggregation process is modeled using a diffusion-reaction equation. The reactivity of the clusters is assumed to depend on the reactivity and number of their particles involved in the aggregation event. The model can be applied to evaluate the aggregation rate constant as a function of the prevailing operating conditions by simply changing the value of the particle stability ratio, without any a priori specification of a diffusion-limited cluster aggregation, reaction-limited cluster aggregation, or transition regime. Furthermore, the model allows one to estimate the structure properties of the formed cluster after the aggregation, based on the computed distance between the aggregating clusters in the final cluster.     

Al-induced crystallization of amorphous ge and formation of fractal ge micro-/nanoclusters

Results on Al-induced crystallization of amorphous Ge (a-Ge) deposited by vacuum thermal evaporation techniques under thermal annealing in N(2) atmosphere are presented in detail. The a-Ge crystallization and fractal Ge pattern formation on the free surface of annealed Al/Ge bilayer films deposited on single-crystal Si (100) substrates were investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive X-ray spectrometry (EDS), and Raman spectra. It is found that the temperature field effects play an extremely crucial role in a-Ge crystallization and fractal Ge formation process. The open branched structure of fractal Ge clusters in Al/Ge bilayer films was effectively prepared by Al-induced crystallization when they were annealed at 400 °C for 60 min. These films with fractal Ge clusters exhibit charming noninteger dimensional nanostructures, which differ from those of conventional integer dimensional materials such as one-dimensional nanowires/nanorods, nanotubes, nanobelts/nanoribbons, two-dimensional heterojunctions, thin films, and zero-dimensional nanoparticles. The SEM image shows that a big Al grain was found located near the center of a fractal Ge cluster after the films were annealed at 400 and 500 °C for 60 min. This suggests that the grain boundaries of polycrystalline Al films are the initial nucleation sites of a-Ge. It also validates the preferred nucleation theory of a-Ge at triple-point grain boundaries of polycrystalline Al at the interface. This discovery may be explained by the metal-induced nucleation (MIN) mechanism.     

Study of Aggregation of Gold Nanoparticles in Chitosan

In this work it is reported the synthesis of gold nanoparticles supported in situ in chitosan by solvated metal atom dispersion technique in order to study the inclusion of Au nanoparticles in the biopolymer matrix. To study their aggregation along time and compare with the synthesis of Au/2-propanol colloid by chemical liquid deposition technique. Studies of Au nanoparticles aggregation along time, supported nanoparticles and colloidal nanoparticles morphology were also carried out. The characterization of Au nanoparticles was performed by transmission electron microscopy, field-emission and scanning electron microscopy, infrared spectroscopy, X-ray diffraction, light scattering and ultraviolet–visible spectroscopy. Metal colloid showed fractal agglomeration type and delay time after the synthesis, the agglomeration size increased to flocculate. Au nanoparticles supported in chitosan showed the same shape as colloids and fractal aggregation was mostly distributed on the matrix.     

Fractal behavior of functionalized fullerene aggregates. I. Aggregation of two-handed tetraaminofullerene with DNA

In tris-buffered saline (TBS) with a trace of dimethylformamide (DMF), the homoaggregation process of a functionalized fullerene, the two-handed tetraaminofullerene (TH), and the heteroaggregation process (complex formation) of TH with DNA (pGL3-control plasmid) were studied dynamically by using a combination of static and dynamic laser light scattering measurements. Fractal behavior was investigated in the aggregation process of both TH homoaggregates and TH-DNA heteroaggregates. The stability of aggregates in solution depends on the molar concentration ratio R(M), defined as the molar ratio of moles of TH to moles of the DNA base pair. Higher R(M) values resulted in lower aggregate stability. The transition of the fractal dimension (Df) in TH homoaggregation by rapidly mixing 3.78 microM TH with an equal volume of the blank buffer was found to vary from a value of 1.46 to 2.02. Dynamic light scattering results revealed that, in the aggregation process, the change in the size distribution of aggregates with time could be related to a Df transition. In the Df transition region, the size distribution of homoaggregates displayed a drastic change from a single-mode distribution to a bimodal distribution, which clearly suggested a restructuring process with the formation of large aggregates. When the aggregation process finally reached equilibrium, Df = 2.02, the size of the homoaggregates had a single mode but a broad distribution. However, TH-DNA heteroaggregation showed a Df transition from 1.58 to 1.7, but over a shorter time range of less than 5 min. Then, the Df value fluctuated in the range of 1.7 and finally reached an equilibrium value of Df approximately 1.78, which was independent of molar concentration. There are two main action forces involved in the heteroaggregation process: van der Waals forces and attractive electrostatic forces, with the latter one being stronger and faster than that of the former. Therefore, a two-step action could occur in the heteroaggregation process. In the beginning of mixing, the attractive electrostatic forces dictated the aggregation process, and then van der Waals forces also got involved in the entire aggregation process. By using an initial concentration of 3.78 microM each and R(M) = 1, TH-DNA heteroaggregates showed more stable solution behavior than the homoaggregates. The lower Df value of the heteroaggregates could be related to a looser compact structure. Results from scanning electron microscopy (SEM) also disclosed the different textures between TH homoaggregates and TH-DNA heteroaggregates; the former had a more dense packing than the latter one.     

The Aggregation Kinetics of Colloidal Particles of Basic Yttrium Carbonate

Studyofthegrowthprocessofcolloidalparticlesofnonequilibriumandirreversibilityisanactiveareaofresearch.Therecognitionofcolloidalaggregatesasfractalobjectshasinspiredalargenumberofexperimentalandtheoreticalstudiesonthestructuralandkineticaspectsofaggregationprocesses"'.Morerecently,kineticsofhematiteaggregationbypolyacrylicacidhavebeenstudiedbyzhangandBume3.Theprimaryhematiteparticleswerequiteuniformandfairlyspherical.Inthispaper,wewillreportthesizeevolutionoffractalaggregatesofinitiallypolydis…     

Gelation dynamics and gel structure of fibrinogen

Gelation dynamics and gel structure of fibrinogen induced by serine protease, thrombin, was investigated by light scattering, real space observation using confocal laser scanning microscopy (CLSM), and turbidity. Effects of additives, such as (linear) saccharides, glucose to dextran, and cyclodextrin, were studied focusing on the interaction with fibrin(ogen) and thrombin. Light scattering measurement was ascertained to be able to characterize the gelation process and growth kinetics. Stepwise (two-step) gelation process, formation of fibrin monomers and protofibrils followed by the lateral aggregation to form fibrin fibers and gel network, was clearly ascertained. Gelation point could be characterized quantitatively. At the gelation point, dynamic light scattering exhibited a self-similar nature of the fibrin gel network, and the fractal dimension was evaluated in good accordance with the reconstructed 3D image of gel network by CLSM. The interaction between the additives and fibrin(ogen) and thrombin were studied by the inhibition test using synthesized substrate. Temporal variation of microstructure of fibrin gel network (lateral fiber growth) was investigated by turbidity in detail. Addition of saccharides affects significantly the network formation as revealed by turbidity. The interaction of dextran with fibrin fibers was examined by fluorescence microscopy, too, and the characteristic spatial distribution was observed.     

Synthesis of polypyrrole micro/nanofibers via a self-assembly process

Novel polypyrrole (PPy) micro/nanofibers were synthesized via a self-assembly process by using 4-hydroxy-3-[(4-sulfo-1-naphthalenyl) azo]-1-naphthalenesulfonic acid (Acid Red B) as dopant and ferric chloride (FeCl₃) as oxidant. Experimental conditions, including the concentration of the dopant, reaction temperature and stirring state have been investigated for their influences on the morphology of the synthesized PPy micro/nanofibers. The products were characterized by scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared spectroscopy. The formation mechanism of micro/nanofibers was studied. It is believed that the micelles formed by the dopant and pyrrole monomer act as templates during the synthesis process. Two functions of aggregation and synthesis are proposed in the reaction system simultaneously, and the morphologies of micro/nanofibers are the co-operations of these two functions. The maximum conductivity value of the PPy micro/nanofibers was 8.56 S cm^?1     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Control over colloidal aggregation in monolayers of latex particles at the oil-water interface

The controlled generation of 2D aggregate networks is studied experimentally using micrometer-sized polystyrene latex particles attached to the oil-water interface. Starting from an initially crystalline monolayer, appropriate combinations of carefully added electrolyte and surfactant enable control over both the fractal dimension and the kinetics of aggregation. Remarkably, the colloidal crystals formed upon first spreading remain stable, even for days, when substantial amounts of electrolyte are added to the aqueous phase. Pressure-area isotherms reveal a slow time evolution of the electrostatic dipole-dipole interaction. When the electrostatic interaction has been sufficiently weakened, aggregation proceeds in well-defined, reproducible manner. The aggregation process is analyzed using quantitative video microscopy. The evolution of the cluster size distribution and its moments is characterized, and static and dynamic scaling exponents are derived to identify the nature of the aggregation process. In the range of concentrations studied here, the kinetics all agree with a "fast", diffusion-limited cluster type of aggregation. However, the fractal dimension strongly depends on the composition of the aqueous subphase. Rather dense structures are found when only electrolyte is used, whereas more open structures are obtained when even small amounts of surfactant are added. It is suggested that this structural dependency is related to the effect of surfactant on the contact angle and its consequences for the anisotropic nature of the capillary interactions.     

A bidimensional simulation of particle-cluster aggregation with variable active sites particles

 In this work a simple program has been developed which simulates the process of particle– cluster aggregation limited by diffusion. All the simulation have been carried out using 2d square lattices with square “particles” having a variable number of active inter-action sites (from 3 to 8) for each particle in order to analyze the effect of such limitation on the fractal dimension of the aggregates. The fractal dimension of such aggregates was calculated by the so-called “box counting” method. It has been shown that there is no change in the value of the fractal dimension (1.70) as the active site number is increased. Instead it appears that there is an average number of active sites of about 2.3 for all the structures no matter how many active interaction sites the particles have. This appears as an interesting result in connection with the aggregation of particles such as renneted casein micelles, which could present differences in the surface density of active sites. Received: 11 February 1997 Accepted: 8 January 1998     

Linear chains and chain-like fractals from electrostatic heteroaggregation

The internal structure of materials prepared by aggregation of oppositely charged polystyrene spheres (electrostatic heteroaggregation) is investigated by static light scattering, optical microscopy, and Brownian dynamics simulation. Light scattering indicates ultralow mass fractal dimensions, as low as 1.2. Such low fractal dimensions, approaching the theoretical limit of a linear object, imply a chaining mechanism. Optical micrographs reveal linear chains with the particle charge alternating down the chains. Brownian dynamics simulation gives additional support for a chaining mechanism. For the polystyrene system (120-nm primary particle diameters), the fractal dimension is found to increase from 1.2 to 1.7 as the background electrolyte is increased. In terms of electrostatic screening, the results match those reported recently for larger polystyrene spheres. The low fractal dimensions appear to represent a crossover from linear chains to a structure of diffusion-limited aggregates; however, experiments under density-neutral conditions imply that sedimentation plays an important role in the formation of ultralow fractal dimensions. The practical implication is that microcomposites with a locally uniform distribution of starting materials and almost any degree of branching can be prepared from oppositely charged particles.     

Destabilization of polystyrene latex particles induced by adsorption of polyvinylamine: mass, size and structure characteristics of the growing aggregates

The obviously visible aggregation of suspended colloidal particles resulting from the addition of polyvinylamine to the aqueous dispersion of polystyrene latex particles bearing surface sulfate groups set in with a delay of 24 h. The aggregation mechanisms and the fractal dimension of the aggregates were derived from the variations with time of the weight and number averaged masses of the aggregates as well as of the weight averaged harmonic mean diameter of the size distribution. Since the establishment of starved layers was determined to be relatively fast and to leave the liquid phase free of polymer, the delay for the obvious destabilization was attributed to the reconformation of adsorbed macromolecules that was expected to be extremely slow. This reconformation promoted the emergence of the diffusion-limited aggregation process that accompanies the permanent reaction-limited aggregation process. The fractal dimension of the latex particles/polyvinylamine aggregates was determined to be 2.12.     

ADDITIVE-INDUCED ENHANCEMENT OF OPTICAL CLARITY OF POLYACRYLAMIDE HYDROGEL

The aqueous polymerization of acrylamide and crosslinking with N,N-methylenebisacrylamide afforded hydrogelsdisplaying high levels of light scattering (poor optical clarity). Enhancement of the optical clarity within a polyacrylamide(PAm) hydrogel was accomplished through the implementation of "refractive index matching". Water-soluble additives wereutilised to better match the refractive index inhomogeneities throughout a given hydrogel. This resulted in lower lightscattering within the system and hence improved clarity. Amino acids, sugars, polymers, and other water-soluble additivessuch as glycerol were investigated by this methodology. Most additives investigaed displayed potential for effectivelyreducing the light scattering within a PAm hydrogel as a function of increased additive concentration. On increasing therefractive index of the water medium, the overall refractive index of a PAm hydrogel was also observed to increase. Thisprovided a quantitative means of determining the effectiveness of a given additive for improving the optical clarity within ahydrogel.     

The cellulose solvent system N,N-dimethylacetamide/lithium chloride revisited: the effect of water on physicochemical properties and chemical stability

The water content in the binary systemN,N-dimethylacetamide/lithium chloride (DMAc/LiCl), acommon cellulose solvent, has been proven to be a crucial parameter. A quickdetermination of water content in DMAc based on the solvatochromism of aUV-active betain probe dye has been developed and validated. An analogousmethod, based on the solvatochromic fluorescence shift ofZelinskij's dye, which strongly depends on thesolventpolarity, was established for water determination in DMAc containing LiCl.Precise physicochemical data of the system DMAc/LiCl, such as density,viscosity, and conductivity, have been obtained. The limiting solubility forLiCl in absolute DMAc is 8.46 wt%. As shown by lightscattering experiments, water in DMAc/LiCl induces aggregation upon standingforlonger periods of time, which is even more prominent for diluted solutions andthose having a poor state of dissolution.     

Facile fabrication of self-assembled PMMA/graphene oxide composite particles and their electroresponsive properties

Core–shell-structured poly(methyl methacrylate) (PMMA)/graphene oxide (GO) composite particles were prepared using a facile process, in which GO was adsorbed spontaneously onto a microspherical PMMA surface when hydrophobic microspheres were dispersed in deionized (DI) water stabilized by amphiphilic GO under ultrasonication. The fabricated composite was characterized by SEM, TEM, FT-IR, and thermogravimetric analysis. Results showed that the particle surface could be wrapped with GO without the need for surfactants. In addition, electrorheological behavior of the chain-forming process of the PMMA/GO composite particles was observed by optical microscopy under an applied electric field. Both shear stress and shear viscosity related to the strength of the applied electric field were measured using a rotational rheometer. The proposed Cho–Choi–Jhon model was used to describe their ER performances for the entire shear rate region. Moreover, the response of the shear stress to an imposed square voltage at a fixed shear rate was also examined.